RUSSIAN ACADEMY OF SCIENCES (RAS) DIVISION OF CHEMISTRY AND MATERIAL SCIENCES RAS

RUSSIAN FOUNDATION FOR BASIC RESEARCH SCIENTIFIC COUNCIL ON ORGANIC CHEMISTRY RAS

ND ZELINSKY INSTITUTE OF ORGANIC CHEMISTRY RAS

International Conference

Molecular Complexity in

Modern Chemistry

MCMC-2014

BOOK OF ABSTRACTS

September 13-19 2014

Moscow Russia

International Advisory Committee

H Alper University of Ottawa Canada

D Astruc University of Bordeaux France

J Dupont Institute of Chemistry Brazil

P J Dyson EPFL Switzerland

R G Finke Colorado State University USA

G C Fu California Institute of Technology USA

A Furstner Max Planck Institut fur Kohlenforschung Germany

V K Jain Bhabha Research Centre India

CW Jones Georgia Institute of Technology USA

P-H Leung Nanyang Technological University Singapore

C Najera Universidad de Alicante Spain

E-i Negishi Purdue University USA

L A Oro University of Zaragoza-CSIC Spain

R Poli Institut National Polytechnique France

V Snieckus Queens University Canada

M Taillefer Institut Charles Gerhardt France

A M Trzeciak University of Wroclaw Poland

Y Yamamoto Tohoku University Japan

Local Organizing Committee

ND Zelinsky Institute of Organic Chemistry RAS

M P Egorov Chairman

V P Ananikov Vice-chairman

A D Dilman

A M Sakharov

A Y Stakheev

AM Starosotnikov

A O Terentev

O V Turova

S G Zlotin

National Advisory Committee

G A Abakumov N Novgorod

I P Beletskaya Moscow

Y N Bubnov Moscow

V N Charushin Ekaterinburg

O N Chupakhin Ekaterinburg

A I Konovalov Kazan

V V Lunin Moscow

V I Minkin Rostov

O M Nefedov Moscow

V N Parmon Novosibirsk

O G Syniashin Kazan

V A Tartakovsky Moscow

B A Trofimov Irkutsk

M S Yunusov Ufa

N S Zefirov Moscow

Index

Plenary Lectures 7

Invited Lectures 22

Oral Communications 60

Posters 110

Authors Index 326

7

Plenary Lectures

8

9

PL1

THE APPLICATION OF PHOTOREDOX CATALYSIS TO NEW

TRANSFORMATIONS IN CHEMICAL SYNTHESIS

DWC MacMillan

Merck Center for Catalysis Princeton UniversityPrinceton NJ 08544

This lecture will discuss the advent and development of new concepts in chemical synthesis

specifically the combination of photoredox catalysis with organic catalysis This new approach to

ldquosynergistic catalysisrdquo will demonstrate that multiple yet separate catalytic cycles can be aligned to

generate activated intermediates that rapidly combine with each other thereby allowing new

approaches to enantioselective CndashC and C-heteroatom bond formation

We will also introduce an approach to the discovery of new chemical reactions that we term

accelerated serendipity Accidental or lsquoserendipitousrsquo discoveries have led to some of the most

important breakthroughs in scientific history many of which have directly affected human life

Given our overarching goal of developing fundamentally new and useful chemical transformations

using catalysis and by acknowledging the tremendous impact of serendipity in scientific discovery

we questioned whether this phenomenon could be forced or simulated and therefore employed as a

tool for reaction discovery

In this presentation we will describe several new transformations that have been discovered via

ldquoaccelerated serendipityrdquo that we expect will find widespread adoption throughout the field of

chemical synthesis Moreover we will further describe how mechanistic understanding of these

processes has led to the design of a valuable new yet fundamental chemical transformation

Acknowledgements Financial support was provided by NIHGMS (R01 01 GM093213-01) and kind gifts from Merck

Amgen and Abbott

10

PL2

GOLD CATALYSIS 20

ASK Hashmi

Organisch-Chemisches Institut Fakultaumlt fuumlr Chemie und Geowissenschaften Universitaumlt

Heidelberg Im Neuenheimer Feld 270 69120 Heidelberg Germany

Homogeneous catalysis by gold has developed to an important sector of catalysis research1

Initially efforts in methodology development clearly dominated in the last years also an increasing

number of applications in synthesis has been reported23

Efforts to understand the basic mechanism

of these reactions continuously accompanied the field4

For twelve years most of the reactions followed simple reaction mechanisms basing on the

interaction of one gold centre in a gold complex or organogold compound with the substrate

molecule In most of these reactions vinylgold or alkylgold intermediates are involved sometimes

also gold carbenoids

Now an entirely new family of reactions basing on the activation of the organic substrates by two

gold complexes at the same time (one -coordinated the other -coordinated) has been discovered

These open up entirely new synthetic possibilities and follow quite complex mechanisms These

mechanisms which are new to the field of organometallic chemistry will be discussed in detail

Some of the new reactions even allow positional selective CH activations of alkyl side chains as

exemplified below

The presentation will also contain results from computational chemistry

References

1 A S K Hashmi Chem Rev 2007 107 3180-3211

2 A S K Hashmi M Rudolph Chem Soc Rev 2008 37 1766-1775

3 M Rudolph A S K Hashmi Chem Soc Rev 2012 41 2448-2462

4 A S K Hashmi Angew Chem Int Ed 2010 49 5232-5241

11

PL3

HOW MUCH CATALYST DO WE NEED

C Bolm

Institute of Organic Chemistry RWTH Aachen University 52056 Aachen Germany

Various C-N- C-O- and C-C-bond forming reactions leading to cross coupling-type products can

be performed without transition metals In this presentation we will discuss cyclizations affording

benzimidazol-2-ones1 and indazoles

2 (eqs 1 and 2 respectively) Photochemical initiations (eq 3)

led us to other directions34

R1 X

NHN

O

R3

R2

N

N

R2

R3

R1

O

40 degC 24 h

X = I Br (Cl F)

(eq 1)

toluene RT 25 h

N

R2

HNR3X

N

N

R2

R3

R1 R1

TMS

O

R2

O

R1hn

CH2Cl2 RT O

O

R1R2

TMS

X = I Br

(eq 2)

(eq 3)

KOHDMSO

diamineK2CO3

Finally we will present mechanochemical activations in ball mills that allow reducing the catalyst

loadings in asymmetric organocatalyses5-7

References

1 a) Yuan Y Thomeacute I Kim S H Chen D Beyer A Bonnamour J Zuidema E Chang

S Bolm C Adv Synth Catal 2010 352 2892 b) Beyer A Reucher C M M Bolm C

Org Lett 2011 13 2876 c) Thomeacute I Bolm C Org Lett 2012 14 1892 d) Beyer A

Buendia J Bolm C Org Lett 2012 14 3948 e) Baars H Beyer A Kohlhepp S V Bolm

C Org Lett 2014 16 536

2 Thomeacute I Besson C Kleine T Bolm C Angew Chem Int Ed 2013 52 7509

3 a) Zhang H-J Becker P Huang H Pirwerdjan R Pan F-F Bolm C Adv Synth Catal

2012 354 2157 b) Becker P Priebbenow D L Zhang H-J Pirwerdjan R Bolm C J

Org Chem 2014 79 814 c) Becker P Priebbenow D L Pirwerdjan R Bolm C Angew

Chem Int Ed 2014 53 269

4 For a photochemical activation in a metal catalysis see Bizet V Buglioni L Bolm C

Angew Chem Int Ed DOI 101002anie201310790

5 a) Joumlrres M Mersmann S Raabe G Bolm C Green Chem 2013 15 612 See also in b)

Kleine T Buendia J Bolm C Green Chem 2013 15 160

6 For a video see httpwwwbeilsteintvtvpostasymmetric-organocatalysis-in-a-ball-mill

7 For a general overview see James S L Collier P Parkin I Hyett G Braga D Maini L

Jones B Friscic T Bolm C Krebs A Mack J Waddell D C Shearouse W C Orpen

G AdamsC Steed J W Harris K D M Chem Soc Rev 2012 41 413

12

PL4

ldquoMOLECULAR METATHESIS CATALYSTSrdquo AT THE DAWN OF

INDUSTRIAL IMPLEMENTATION

DE Fogg

University of Ottawa

Ruthenium-catalyzed olefin metathesis has enormous potential for impact on the chemical

enterprise in sectors ranging from pharma to specialty polymers and ldquogreenrdquo feedstocks

Phosphine-free metathesis catalysts particularly those of the Hoveyda type (HII see Figure 1)

occupy a position of increasing prominence In one of the most high-profile current applications of

metathesis chemistry transformation of seed oils into functionalized olefins HII significantly out-

performs the benchmark Grubbs catalyst GII [12]

despite the fact that the two catalysts generate a

common active species (A) Reports from pharma RampD indicate that HII also offers superior

performance in some demanding RCM applications (RCM = ring-closing metathesis)[3]

As these

and closely related molecular metathesis catalysts enter deployment in process chemistry

understanding the mechanistic basis of their performance takes on added importance

We will discuss potential contributors to the improved productivity of HII the absence of free

PCy3 the presence of the styrenyl ether ligand and operation of HII via interchange-associative

pathways The relevance of each of these factors will be considered in the context of demanding

ring-closing and cross-metathesis reactions

Figure 1 Molecular structure of an organometallic product

References

[1] Miao X Fischmeister C Dixneuf P H Bruneau C Dubois J L Couturier J L Green

Chem 2012 14 2179-2183

[2] Biermann U Bornscheuer U Meier M A R Metzger J O Schafer H J Angew Chem

Int Ed 2011 50 3854ndash3871

[3] van Lierop B J Lummiss J A M Fogg D E Ring-Closing Metathesis A How-To Guide

In Olefin Metathesis Theory and Practice Grela K Ed Wiley Weinheim 2014

13

PL5

REDUCTIONS WITH ORGANIC REAGENTS mdash THE ELECTRON AS A

CATALYST

A Studer

WWU Muenster Chemistry Germany

In the lecture reduction processes for generation of various radicals using different organic reagents

will be presented Reactions are generally conducted using stoichiometric SET-reagents However

also some catalytic variants will be presented In the presentation radical perfluoroalkylations and

azidations will be addressed Moreover the concept of using the electron as a catalyst will be

discussed and some examples provided

14

PL6

NANOELECTRONICS MOLECULAR METAL WIRES AND RELATED

MOLECULAR MATERIALS

SM Peng

Department of Chemistry National Taiwan University Taipei Taiwan

We have designed a series of new ligands such as oligo-α-pyridylamines and used them to

construct an unique class of quadruple helix of metal strings This achievement leads to a new

direction to the application of molecular wires in the nanoelectronics

The outline is as follows

I Linear Metal String Complexes (1)

Synthesis Structure Bonding

II Potential Application as Molecular Metal Wires amp Molecular Switches (2)

STM-bj Study on the Conductivity of Metal Strings

Comparative Study on the I-V Characterisics (Theory VS Experiment)

III Tuning of the Metal Strings (3-9)

Naphthyridyl Amino Ligands Low Oxidation Mixed Metal Strings

Asymmetrical Ligands Toward Molecular Rectifier

Heteronuclear Metal String Complexes

Chiral Quadruple Helixes

IV Conclusion

Fig1 Metal Strings of Oligo- -pyridylamido Ligands

1 C-Y Yeh C-C Wang Y-H Chen and S-M Peng in Redox Systems Under Nano-Space

Control Ed T Hirao Springer Germany 2006 Ch 5

2 I-W P Chen M-D Fu W-H Tseng J-Y Yu S-H Wu C-J Ku C-H Chen and S-M

Peng Angew Chem Int Ed Engl 2006 5414

3 (a) C-H Chien J-C Chang C-Y Yeh G-H Lee J-M Fang and S-M Peng Dalton Trans

2006 2106 (b) C-H Chien G-H Lee Y Song and S-M Peng Dalton Trans 2006 3249

4 M-M Rohmer I P-C Liu J-C Lin M-J Chiu C-H Lee G-H Lee M Benard X Lopez

S-M Peng Angew Chem Int Ed Engl 2007 46 3533

5 I P-C Li W-Z Wang and S-M Peng Chem Commun 2009 4323-4331

6 R H Ismayilov W-ZWang G H Lee C Y Yeh S A Hua Y Song M M Rohmer M

Beacutenard S-M Peng Angew Chem Int Ed 2011 50 2045-2048

7 I P-C Liu C-H Chen S-M Peng Bull Jpn Soc Coord Chem 2012 59 1-8

N N N N N

M M M M MX X

4

m

M = N i C o C r

m = 0 1 2 3

X = C l N C S

15

8 M-C Cheng C-L Mai C-Y Yeh G-H Lee S-M Peng Chem Commun 2013 49 7938-

7940

9 M-J Huang S-A Hua M-D Fu G-C Huang C Yin C-H Ko C-K Kuo C-H Hsu G-H

Lee K-Y Ho C-H Wang Y-W Yang I-C Chen S-M Peng C-h Chen Chem Eur J

2014 DOI 101002chem201400067

16

PL7

NEW CYCLOADDITION STRATEGIES BASED ON STRAINED AND

UNUSUAL MOLECULES

RL Danheiser

Department of Chemistry Massachusetts Institute of Technology Cambridge MA 02139 USA

Highly substituted carbocyclic and heterocyclic rings are key structural features in many

biologically significant and commercially important compounds Although classical synthetic

approaches to such compounds have generally relied on linear substitution strategies convergent

cycloaddition and annulation strategies have emerged as powerful alternative methods for the

assembly of highly substituted cyclic compounds The intrinsic convergent nature of cycloaddition

and annulation strategies facilitates the efficient assembly of highly substituted systems that would

have required long multistep routes using alternative methods

This talk will focus on the application of strained and unusual molecules as building blocks in

cycloaddition strategies for the construction of complex carbocyclic and heterocyclic compounds

The synthetic utility of highly unsaturated conjugated molecules such as vinylketenes conjugated

enynes vinylallenes allenylimines and iminoacetonitriles will be described as well as their

application in the total synthesis of natural products

17

PL8

SILICON TETHER MOTIF IN C-H ACTIVATION REACTIONS

V Gevorgyan

University of Illinois at Chicago

We have developed a set of new transition metal-catalyzed C-H activation methodologies

employing a silicon-tether motif These methods feature (a) use of silyl group as a tether between a

substrate and a reagent thus transforming intermolecular reaction into intramolecular reaction1-2

(b) employment of a silicon-tethered directing group which is traceless or easily convertable into

valuable functionalities3-8

(c) use of silyl-tethered hydrosilane reagent9-10

and (d) introduction of

new NSi-chelation concept that allows for a remote activation of aliphatic C-H bonds11

The scope of these transformations will be demonstrated and the mechanisms will be discussed

References

1 Huang C Gevorgyan V J Am Chem Soc 2009 131 10844

2 Huang C Gevorgyan V Org Lett 2010 12 2442

3 Chernyak N Dudnik A S Huang C Gevorgyan V J Am Chem Soc 2010 132 8270

4 Dudnik A S Chernyak N Huang C Gevorgyan V Angew Chem Int Ed 2010 49 8729

5 Huang C Chattopadhyay B Gevorgyan V J Am Chem Soc 2011 133 12406

6 Huang C Ghavtadze N Chattopadhyay B Gevorgyan V J Am Chem Soc 2011 133 17630

7 Gulevich A V Melkonyan F S Sarkar D Gevorgyan V J Am Chem Soc 2012 134

5528

8 Sarkar D Melkonyan F S Gulevich A V Gevorgyan V Angew Chem Int Ed 2013 52

10800

9 Kuznetsov A Gevorgyan V Org Lett 2012 14 914

10 Kuznetsov A Onishi Y Inamoto Y Gevorgyan V Org Lett 2013 15 2498

11 Ghavtadze N Melkonyan F S Gulevich A Huang C Gevorgyan V Nat Chem 2014 6

122

18

PL9

WERNER COMPLEXES A NEW CLASS OF CHIRAL HYDROGEN BOND

DONOR CATALYSTS FOR ENANTIOSELECTIVE ORGANIC REACTIONS

JA Gladysz

Department of Chemistry Texas AampM University PO Box 30012 College Station Texas 77842-

3012 USA

Salts of the chiral tris(ethylenediamine)-substituted octahedral trication [Co(en)3]3+

and related

species have played important historical roles in the development of inorganic chemistry and

stereochemistry12

As Werner described in 1912 the two enantiomers commonly designated and

can be separated by crystallization of the diastereomeric tartrate salts2 However despite the low

cost and ready availability of the building blocks there have been no applications in

enantioselective organic synthesis

NH2

NH2

H2N

H2N

NH2

H2N

Co3+

H2N

H2N

NH2

NH2

NH2

H2N

Co3+L D

We have found that [Co(en)3]

3+ and related cations can be rendered soluble in organic solvents by

using lipophilic anions such as BArfndash

3 Suitably functionalized derivatives act as highly

enantioselective catalysts for a variety of carbon-carbon bond forming reactions The mechanisms

involve outer sphere activation of the electrophile by hydrogen bonding to the NH moieties Other

types of metal-containing chiral hydrogen bond donors are also effective including a chelate of the

CpRuL fragment

H2N

H2N

NH2

NH2

NH2

H2N

Co3+ Ph

Ph

Ph

Ph

Ph

Ph

2Clndash BAr fndash

catNO2

NO2

OMe

O

MeO

O

Et3N acetone

10 molO O

OMeMeO

12 eq 0 degCX

X

Time (h)

Conversion ()

ee ()

15 gt99 88NO2

OMe

O

MeO

O

22 98 94NO2

OMe

O

MeO

O

O

Ph

H2N

H2N

NH2

NH2

NH2

H2N

Co3+ Ph

Ph

Ph

Ph

Ph

Ph

2BF4ndash BAr f

ndash

H2N

H2N

NH2

NH2

NH2

H2N

Co3+ Ph

Ph

Ph

Ph

Ph

Ph

2PF6ndash BAr f

ndash

Time (h)

Conversion ()

ee ()

10 94 90

7 98 97

Time (h)

Conversion ()

ee ()

4 gt99 86

4 gt99 94

L L L

1 Kauffman G B Coord Chem Rev 1974 12 105-149

2 Werner A Chem Ber 1911 44 1887-1898 and 1912 45 121-130

3 Ganzmann C Gladysz J A Chem Eur J 2008 14 5397-5400

4 Ghosh S K Ojeda A S Guerrero-Leal J Bhuvanesh N Gladysz J A Inorg Chem 2013

52 9369-9378

5 Thomas C Gladysz J A ACS Catalysis 2014 5 1134-1138

19

PL10

COMPLEXITY IN SIMPLICITY THE PROTOTYPE REACTIONS OF

CARBENE ANALOGS

MP Egorov

Zelinsky Institute of Organic Chemistry Russian Academy of Sciences Leninsky Prospect 47

Moscow 119991 Russia

20

PL11

SELECTIVELY ALKYLATED AND ARYLATED N-HETEROAROMATICS

VIA ACCEPTORLESS DEHYDROGENATIVE CONDENSATION

(ADC) REACTIONS

R Kempe

Lehrstuhl Anorganische Chemie II (Catalyst Design)University of Bayreuth Bavaria Germany

Dwindling reserves of crude oil and the resulting price increase of this and other fossil carbon

sources combined with environmental concerns have resulted in a call for the use of alternative

preferably renewable resources Aside from fuel ultimately a wide variety of chemical feedstocks

are derived from fossil sources Renewable lignocellulosic materials are indigestible and therefore

not useful as food products and can be processed to give alcohols and polyols These rather highly

oxidized hydrocarbons differ drastically in their chemical nature from the cracking products of

crude oil Thus there is a high demand for new reactions that utilize alcohols and convert them into

key chemicals Recently our group developed a sustainable catalytic pyrrole synthesis[1]

Secondary alcohols and amino alcohols are deoxygenated and linked selectively via the formation

of CndashN and CndashC bonds Two equivalents of hydrogen gas and two equivalents of water are

eliminated in the course of the reaction (Acceptorless Dehydrogenative Condensation ADC)

Alcohols based entirely on renewable resources can be used as starting materials The catalytic

synthesis protocol tolerates a large variety of functional groups which includes olefins chlorides

bromides organometallic moieties amines and hydroxyl groups Furthermore we have developed a

catalyst that operates efficiently under mild conditions This methodology could also be used to

synthesize selectively functionalized pyridines from alcohols[2] In the talk the development of

alcohol re-functionalization reactions and the design of catalyst systems that mediate these reactions

are discussed

[1] S Michlik R Kempe Nature Chem 2013 5 140

[2] S Michlik R Kempe Angew Chem Int Ed 2013 52 6450

21

PL12

THE CATALYST TODAY BIG BANG AND LIFE AFTER

IP Beletskaya

Lomonosov Moscow State University Department of Chemistry Moscow Russia

Nanocatalysis and catalysis by Lewis and Broensted acids will be considered in the lecture

22

Invited Lectures

23

24

IL1

CYCLIZATIONS OF ALKYNES FROM STEREOELECTRONICS TO

CASCADE TRANSFORMATIONS

IV Alabugin

Department of Chemistry and Biochemistry Florida State University Tallahassee Fl

One of the simplest organic functional groups the alkyne moiety is also one a useful starting point

for the design of cascade transformations which proceed through the formation of multiple C-C C-

H C-N and C-O bonds [1] In this talk I will illustrate how the revised stereoelectronic rules for

alkyne cyclizations [2] can be used for the bottom-up preparation of carbon nanostructures for

molecular electronics (ie graphene nanoribbons) In our approach alkyne chains of varying sizes

shapes and functionalities are built in a modular fashion and ldquozippedrdquo up into graphene

substructures via controlled cascades of all-exo or all-endo cyclizations [3]

Even in the presence of multiple functionalities alkyne cascades can be made chemoselective via

kinetic self-sorting of the pool of equilibrating radicals [4] Further synthetic opportunities are

presented by fusion of cyclization cascades with self-terminating fragmentations that allow use of

alkenes as synthetic equivalents of alkynes [5]

[1] Alabugin I V Gold B J Org Chem 2013 78 7777

[2] Alabugin I V Gilmore K Manoharan M J Am Chem Soc 2011 133 12608 Alabugin I

V Gilmore K Chem Commun 2013 49 11246

[3] Byers P M Rashid J I Mohamed R K Alabugin I V Org Lett 2012 14 6032 Byers

P J Am Chem Soc 2012 134 9609

[4] Mondal S Mohamed R K Manoharan M Phan H Alabugin I V Org Lett 2013 15

5650

[5] Mondal S Gold B Mohamed R K Alabugin I V Chemistry ndash Eur Journal 2014 in

print

25

IL2

ARTIFICIAL PHOTOSYNTHESIS USING TRANSITION METAL

COMPLEXES

O Ishitani

Department of Chemistry Tokyo Institute of Technology Japan

Both the problems of the global warming and shortage of the fossil fuels have brought about great

interest in photochemical utilization of CO2 with solar energy Efficient photocatalysts for CO2

reduction must be necessary for development of such an important technology

We have developed novel types of photocatalytic systems using metal complexes andor

semiconductors as a photocatalyst1 In this presentation I will focus on the architecture of two

types of the photocatalysts using transition metal complexes

(1) A mixed photocatalytic system including a ring-shaped Re(I) multinuclear complex as a

photosensitizer2

(2) Ru(II)-Re(I) and Ru(II)-Re(I) supramolecular photocatalysts3

The efficiency of the former photocatalytic system has been highest in the reported CO2-reduction

photocatalysts ( = 82) and the latter photocatalysts have been most robust (TON gt 3000)

References

1 (a) Yui T Tamaki Y Sekizawa K Ishitani O Photocatalytic reduction of CO2 from

molecules to semiconductors Top Curr Chem 2011 303 151-84 (b) Sekizawa K Maeda K

Domen K Koike K Ishitani O J Am Chem Soc 2013 135 4596

2 Morimoto T Nishiura C Tanaka M Rohacova J Nakagawa Y Funada Y Koike K

Yamamoto Y Shishido S Kojima T Saeki T Ozeki T Ishitani O J Am Chem Soc

2013 135 13266

3 (a) Gholamkhass B Mametsuka H Koike K Tanabe T Furue M Ishitani O Inorg

Chem 2005 44 2326 (b) Sato S Koike K Inoue H Ishitani O Photochem Photobiol Sci

2007 6 454 (c) Koike K Naito S Sato S Tamaki Y Ishitani O J Photochem Photobiol

A Chem 2009 207 109 (d) Tamaki Y Watanabe K Koike K Inoue H Morimoto T

Ishitani O Faraday Discuss 2012 155 115 (e) Tamaki Y Morimoto T Koike K Ishitani

O Proc Natl Acad Sci USA 2012 109 15673 (f) Tamaki Y Koike K Morimoto T

Ishitani O J Cat 2013 135 22 (g) Tamaki Y Koike K Morimoto T Yamazaki Y

Ishitani O Inorg Chem 2013 52 11902

26

IL3

A PARADIGM FOR THE PRACTICAL AND ECONOMICAL FORMATION

OF CARBONmdashCARBON AND CARBONmdashHETEROATOM BONDS

ORGANOCATALYTIC REDOX COUPLED TRANSITION METAL

CATALYZED DEHYDRATIVE BOND CONSTRUCTIONS

LS Liebeskind MG Lindale

Emory University Department of Chemistry Atlanta Georgia USA

The current world-wide focus on C-H functionalization is driven in part by the conceptual promise

of atom-efficient sustainable syntheses from readily available feedstocks Of equal conceptual

value is the dehydrative formation of CmdashC CmdashN and CmdashO bonds from common bioavailable

hydroxylic reactants like carboxylic acids alcohols and phenols Given the sustainable generation

of hydroxylic feedstocks dehydrative bond formations can impact all levels of synthesis

(commodities fine chemicals biologicals) if they are efficient economical practical and substrate

general And they are uniquely poised to contribute to the search for the sustainable conversion of

biomass to biofuels This lecture describes a paradigm for the conversion of hydroxylic reactants to

value-added CmdashC CmdashN and CmdashO products based on a practical organocatalytic redox-coupled

transition metal catalyzed dehydrative bond forming process

27

IL4

CHEMICAL SYNTHESIS USING AMPHOTERIC MOLECULES

AK Yudin

University of Toronto

Over the past seven years my lab has been exploring the use of amphoteric molecules in chemical

synthesis What started as a curiosity-driven project has turned into a sustained exploration of a

virtually untouched segment of chemistry characterized by molecules with unusual combinations of

functional groups The multifunctional nature arising from forced orthogonality enables amphoteric

molecules to participate in reactions of high atom- and step- economy thereby enabling efficient

syntheses characterized by minimal reliance on protecting groups

In this lecture I will illuminate several classes of reagents developed in our lab I will discuss the

discovery of bench-stable aldehydes equipped with a C-B bond at the alpha position These

intriguing molecules have enabled the synthesis of a rich palette of other reagents that contain

carbon-boron bonds at strategic positions With the growing repertoire of boron-containing

amphoteric molecules we are in a good position to explore ideas that range from reaction discovery

to the synthesis of boron-based biologically active compounds

I will also present the evolution of peptide macrocyclization technology driven by amphoteric

aziridine aldehydes As part of this study we are attempting to understand the conformational

preferences of peptide macrocycles As a result we are moving closer to our ultimate goal of

rationalizing the behavior of a wide range of substrate classes in our cyclization reactions as well as

understanding cellular activity of macrocycles I will conclude my talk with a discussion of our

integrative macrocyclization approaches and will present recent results of our protein crystallization

efforts

28

IL5

EMERGENT FUNCTION FROM COMPLEX ADAPTIVE CATALYSTS

VV Fokin

The Scripps Research Institute Department of Chemistry La Jolla California USA and Moscow

Institute of Physics and Technology Dolgoprudny Russia

Exploiting the versatility of catalytic processes requires rigorous interrogation of the constantly

changing environment of the catalyst Detailed understanding of critical events affecting a catalyst

such as activation and deactivation unproductive off-cycle pathways and changes in the nature of

dominant species are of critical importance The seemingly formidable challenge of controlling the

reactivity of complex catalytic systems that involve dynamic and rapidly equilibrating mixtures of

intermediates may in fact be their advantage well-defined (ie non-adaptable) catalysts are often

inefficient when compatibility with many functional groups and conditions is the goal

Examples of investigation of such catalytic reactions will be illustrated by case studies of transition

metal-catalyzed transformations of alkynes Alkynes are among the most energetic hydrocarbons

and transition metals enable selective and controlled manipulation of the triple bond revealing their

unique reactivity transformations of alkynes into heterocycles and into a variety of molecules with

new carbonndashheteroatom bonds These seemingly simple transformations involve an impressive

variety of intermediates yet proceed with high selectivity and efficiency maintaining their reactivity

in most complex environments such as the biological milieu of living organisms

29

IL6

RAPID PHOTOASSISTED ACCESS TO sp3-RICH POLYHETEROCYCLIC

SCAFFOLDS

OA Mukhina NNB Kumar WC Cronk WJ Umstead AG Kutateladze

Department of Chemistry and Biochemistry University of Denver USA

Photochemical reactions hold unparalleled promise for building prohibitively strained carbo‐ and

heterocyclic scaffolds which offer expeditious access to difficult synthetic targets not accessible via

ground state chemistry Yet photochemistry is underutilized by the synthetic community which is

especially true for Diversity Oriented Synthesis (DOS) In this context we have been developing a

new photoassisted synthetic methodology which will enhance synthetic chemistry toolbox and will

be compatible with DOS1 This new photoassisted synthetic methodology allows for rapid access

to topologically diverse polycyclic scaffolds decorated by various functional groups and

carboheterocyclic pendants rigidly or semi-rigidly held in a unique spatial configuration by these

novel core frameworks Access to such topologically diverse scaffolds is realized via key

photochemical steps and their combination with ground state reactions most prominently via the

recently discovered intramolecular cycloaddition reactions of azaxylylenes and quinomethanes

photogenerated via excited state intramolecular proton transfer Details of an experimental and

theoretical mechanistic study to gain deeper understanding of underlying processes in the excited

states will also be discussed

A typical example of rapid growth of complexity in a photoassisted synthesis of enantiopure

conformationally locked ribofuranosylamines spiro-linked to oxazolidino-diketopiperazines via a

straightforward ldquoassemblyrdquo of a threonine-based photoprecursor photochemical transformation

and a simple post-photochemical modification is shown below

[1] (a) Mukhina OA Kumar NNB Arisco TM Valiulin RA Metzel GA Kutateladze

AG Angew Chem Int Ed 2011 50 9423-9428 (b) Nandurkar NS Kumar NNB

Mukhina OA Kutateladze AG ACS Combinatorial Sci 2013 15 73-76 (c) Kumar

NNB Mukhina OA Kutateladze AG J Am Chem Soc 2013 135 9608-9611 (d)

Cronk WC Mukhina OA Kutateladze AG J Org Chem 2014 791235-1246

30

IL7

TRANSITION METAL CLUSTERS UNAVOIDABLE CONTAMINANTS OR

IMPORTANT PLAYERS IN SOLUTION

VP Ananikov

Zelinsky Institute of Organic Chemistry Russian Academy of Sciences Leninsky Prospect 47

Moscow 119991 Russia Department of Chemistry Saint Petersburg State University Stary

Petergof 198504 Russia

Application of transition metal catalysis in organic synthesis is an area of outstanding progress with

prominent achievements in carbon-carbon cross-coupling carbon-heteroatom bond formation and

atom-economic construction of organic molecules

Mechanistic studies have revealed two different frameworks for catalytic processes in solution

depending on the nature of selected system and on the type of catalyst precursor used single type

metal species catalysis or multiple metal species catalysis [1] The first type of systems is widely

utilized and it is based on well-defined metal complex with strongly bound ligands The catalyst

precursor undergoes only partial or minor chemical modifications prior entering the catalytic cycle

In this model the formation of other metal derivatives is not facilitated and the active core of the

catalyst is preserved throughout the catalytic cycle

The second model can be considered as multiple metal species catalysis (in some cases - ldquococktailrdquo

of catalysts) and involves a range of simultaneously present and dynamically interchangeable metal-

containing species such as metal complexes clusters and nanoparticles [2] Such mechanistic

picture may be expected when in situ generated catalysts are employed or upon usage of

nanoparticles as catalysts precursors

It is of much interest to reveal the role of metal clusters in these catalytic systems Formation of

clusters was detected in many cases although their role remains unclear In some cases the presence

of clusters was related to decomposition of the active form while in the other cases the formation of

dinuclear and polynuclear species is an important stage of catalyst evolution in solution

We have investigated soluble metal complexes and nanoparticles of Pd Ni Pt and Au for

development of efficient catalytic systems for selective carbon-heteroatom and carbon-carbon bond

formation in solution [3-5] Homogeneous transition-metal-catalyzed reactions and heterogeneous

nanoparticle-catalyzed reactions were considered with a focus on metal species interconversions

and nanoparticle contamination of homogeneous catalytic systems

References

[1] Kashin AS Ananikov V P J Org Chem 2013 78 11117 (doi 101021jo402038p)

[2] Ananikov V P Beletskaya I P Organometallics 2012 31 1595 (doi 101021om201120n)

[3] Zalesskiy S S Sedykh A E Kashin A S Ananikov V P J Am Chem Soc 2013 135

3550 (doi 101021ja311258e)

[4] Ananikov V P Orlov N V Zalesskiy S S Beletskaya I P Khrustalev V N Morokuma

K Musaev D G J Am Chem Soc 2012 134 6637 (doi 101021ja210596w)

[5] Kashin A S Ananikov V P Top Catal 2013 56 1246 (doi 101007s11244-013-0091-5)

31

IL8

SIMPLE COPPER CATALYSTS FOR C-C C-N AND C-O BONDS

FORMATION

F Monnier

Institut Charles Gerhardt (UMR 5253) ENSCM FRANCE

Since its renaissance in 2001 [1] the copper cross-coupling of nucleophiles with aryl halides has

been increasingly studied [2] In this account we exposed our last contribution for the formation of

C-C [3] C-N [4] and C-O [5] bonds catalyzed by a cheap and simple combination of copper salts

and -diketone ligands

1 a) M Taillefer H-J Cristau P P Cellier J-FSpindler Env SAU2001-1009 and SAU2001-

01044 patents Fr2833947-WO0353225 (Pr Nb Fr 2001 16547) M Taillefer H-J Cristau P

P Cellier J-F Spindler A Ouali Fr2840303-WO03101966 (Pr Nb Fr 2002 06717) b) S L

Buchwald A Klapars J C Antilla G E Job M Wolter F Y Kwong G Nordmann E J

HennessyWO02085838 (priority number US0286268 2001)

2 For a review see F Monnier M Taillefer Angew Chem Int Ed 2009 48 6954-697

3 a) G Danoun A Tlili F Monnier M Taillefer Angew Chem Int Ed 2012 51 12815 b)

MTaillefer F Monnier A Tlili G Danoun PCT Int Appl (2013) WO 2013 EP61697

20130606 FR20120055275 20120606

4 a) A Tlili F Monnier M Taillefer Chem Commun 2012 48 6408-6410 b) E Racine F

Monnier J-P Vors M Taillefer Chem Commun 2013 49 7412 c) E Racine F Monnier J-

P Vors M Taillefer Org Lett 2011 13 2818

5 a) A Tlili N Xia F Monnier M Taillefer Angew Chem Int Ed 2009 48 8725-8728

32

IL9

INTERACTIONS IN IONIC LIQUIDS PROBED BY NMR SPECTROSCOPY

DISTANCES CONFORMATIONS AND MORE

R Giernoth A Broehl Y Lingscheid

University of Cologne Department of Chemistry Koeln Germany

One often-mentioned aspect of ionic liquids (ILs) is that they are ldquodesigner solventsldquo whose

properties can be designed for any particular need [1] Obviously it is impossible to choose a

different property for a given IL but only a different IL entirely To be able to sensibly do so it is

necessary to know about the supramolecular structures and the governing interactions in the ionic

liquid phase

NMR spectroscopy and the nuclear overhauser effect

spectroscopy (NOE) in particular is the method of choice

for the investigation of ion pair interactions [2] The

NOE arises due to inter- and intramolecular cross

relaxation

To be able to precisely measure interactions in solution

an internal distance standard is needed We have

synthesized a monofluorinated ionic liquid which was subsequently employed in NOE-based NMR

investigations for the determination of distances and interactions in the ionic liquid phase

In a different project we are studying the influence of

different ionic liquids on peptide conformations much

in accord with the well-known Hofmeister series of ions

[3] With the help of a model system we are going to

demonstrate that the choice of ions has a strong effect on

the tertiary structure of different peptides in solution

and how these effects can be used for new non-native

peptide chemistry

References

[1] for reviews see JP Hallett T Welton Chem Rev 2011 111 3508-3576 E J Maginn J

Phys Condens Matter 2009 21 1ndash17

[2] P S Pregosin Pure Appl Chem 2009 81(4) 615ndash633 Y Lingscheid S Arenz R Giernoth

ChemPhysChem 2012 13 261ndash266

[3] F Hofmeister Arch Exp Pathol Pharmakol 1888 64 247

33

IL10

APPLICATION OF α-CF3-SUBSTITUTED DIAZOCOMPOUNDS IN

ORGANIC SYNTHESIS AND CATALYSIS

SN Osipov DV Vorobyeva IE Tsishchuk

AN Nesmeyanov Institute of Organoelement Compounds Russian Academy of Sciences Moscow

An efficient pathway to multifunctional CF3-containing aromatic heteroaromatic and heterocyclic

compounds including cyclic amino carboxylic and amino phosphonic acid derivatives have been

developed The method is based on in situ generation of highly electrophilic CF3-carbene species

from the corresponding α-diazo carboxylates or phosphonates under Cu- or Rh-catalysis and their

reactions with appropriate nucleophilic partners1-4

The further applications of the reaction products in metal-catalysed transformations of different

types eg such as ring closing diene and ene-yne metathesis intramolecular Pauson-Khand

reaction as well as [2+2]-cycloaddition open an access to new families of fluorinated molecules

References

1 DV Vorobyeva AK Mailyan AS Peregudov NM Karimova TP Vasilyeva IS

Bushmarinov C Bruneau PH Dixneuf SN Osipov Tetrahedron 2011 67 3524

2 AK Mailyan IM Krylov C Bruneau PH Dixneuf SN Osipov Synlett 2011 2321

3 AK Mailyan IM Krylov C Bruneau PH Dixneuf SN Osipov Eur J Org Chem

2013 5353

4 IE Tsishchuk DV Vorobyeva AS Peregudov SN Osipov Eur J Org Chem 2014

2480

34

IL11

NEW ADVANCES IN ORGANOMETALLIC AND PHOSPHORUS

ELECTROCHEMISTRY

DG Yakhvarov OG Sinyashin

AEArbuzov Institute of Organic and Physical Chemistry Laboratory of Organometallic and

Coordination Compounds Kazan Russian Federation

The development of modern chemical science and creation of new industrially applicable

technologies are focused on application of effective and ecologically safe methods for the

preparation of important and useful chemical compounds and materials The combination of

transition-metal catalysis and organic electrosynthesis has attracted increasing attention due to the

high selectivity and efficiency of this approach in the synthetic preparation of various compounds

bearing carbon-carbon and carbon-element bonds The mild conditions single-stage process cyclic

regeneration of the catalyst and convenient and relatively inexpensive form of the energy used are

the main advantages of electrochemical methods Application of electrochemical processes to large-

scale production (macroscale synthesis) has led to significant development of the chemical

technologies of the 21st century due to easy access to highly reactive intermediates and tuning of

the reactivity of the substrate used during the synthetic process by simple adjustment of the

electrode potential

The elaborated in our research group electrochemical methods have been successfully applied for

generation of organometallic sigma-complexes1 which are important intermediates of different

carbon-carbon and carbon-element coupling processes selective preparation of organophosphorus

compounds from white phosphorus2 activation of inert oligophosphorus moieties formed in the

coordination sphere of transition metal complexes3 selective cleavage of the tungsten-phosphorus

bond resulting in valuable metal-free phosphorus heterocycles obtained via phosphinidene

intermediates4

Herein we present recent advances in synthetic application of the electrochemical techniques for

preparation and activation of organonickel complexes1 and generation of new previously known as

unstable phosphorus intermediates5 which can be applied for preparation of practically useful

organophosphorus compounds transition metal catalysts and magnetically active materials6

Acknowledgements Financial support from the Russian Scientific Fund (project 14-13-01122) and

Russian Foundation for Basic Research (project 09-03-00933-a) is gratefully acknowledged

References

[1] DGYakhvarov AFKhusnuriyalova OGSinyashin Organometallics 2014 in press

[2] DGYakhvarov EVGorbachuk OGSinyashin Eur JInorgChem 2013 4709

[3] DYakhvarov PBarbaro LGonsalvi SMantildeas SMidollini AOrlandini MPeruzzini

OSinyashin FZanobini Angew Chem Int Ed 2006 45 4182

[4] DGYakhvarov YuHBudnikova NHTran Huy LRicard FMathey Organometallics

2004 23 1961

[5] DYakhvarov MCaporali LGonsalvi ShLatypov VMirabello IRizvanov OSinyashin

PStoppioni MPeruzzini Angew ChemIntEd 2011 50 5370

[6] DYakhvarov ETrofimova OSinyashin OKataeva PLoumlnnecke EHey-Hawkins APetr

YuKrupskaya VKataev RKlingeler BBuumlchner Inorg Chem 2011 50 4553

35

IL12

TRIFLUOROMETHYLATION BY SUNLIGHT-PROMOTED

PHOTOREDOX CATALYSIS

T Koike M Akita

Tokyo Institute of Technology Chemical Resources Laboratory Yokohama Japan

Photoredox catalysis 1 mediated by photo-sensitizers (eg [Ru(bipy)3]

2+ and relevant Ir complexes)

has attracted increasing attention as practical green synthetic chemical processes because they are

visible light-promoted redox-neutral reactions

We have demonstrated that photoredox catalysis is a powerful synthetic tool in particular for

trifluoromethylation of olefinic substrates which is the topic of the presentation23

In all cases

electron transfer from the photoexcited metal species to an electrophilic CF3-reagent generates the

key CF3 radical intermediate together with the cationic species of the catalyst Subsequent

addition of the CF3 radical to the olefinic substrate followed by oxidation of the resultant carbon

radical intermediate by the cationic metal species gives the carbocationic intermediate which is

trapped by nucleophiles or deprotonated to furnish the coupling products The sequential redox

processes make the system redox-neutral It is remarkable that the reactions are promoted not only

by artificial light sources (eg Xe lamp and blue LED lamps) but also by sunlight

References 1) C K Prier D A Rankic and D W C MacMillan Chem Rev 113 5322 (2013)

2) T Koike and M Akita (a) Synlett 24 2492 (2013) (b) Topics in Cat 259 in press (2014)

(DOI 101007s11244-014-0259-7) 3) Y Yasu T Koike M Akita et al (a) Angew Chem Int

Ed 51 9567 (2012) (b) Chem Commun 49 2037 (2013) (c) Org Lett 15 2136 (2013) (d)

Org Lett 16 in press (2014) (DOI 101021ol403500y) (e) Beilstein J Org Chem submitted

(f) to be submitted see also (g) Chem Commun 48 5355 (2012) (h) ibid 49 7249 (2013)

36

IL13

CYCLIC HYPERVALENT IODINE REAGENTS A TREASURE OF

REACTIVITY FOR CATALYSIS AND SYNTHESIS

J Waser

Ecole Polytechnique Federale de Lausanne ISIC SB LCSO Lausanne Switzerland

The non-classical four electrons three centers bonds of hypervalent iodine are weaker than normal

classical bonds This confers an exceptional reactivity to these compounds as oxidants or atom-

transfer reagents Cyclic hypervalent iodine reagents are especially interesting as they combine

enhanced stability with unique opportunities for reactivity modulation In particular our group has

been interested in the development of alkynylation methods using cyclic EthynylBenziodoXolone

(EBX) hypervalent iodine reagents1 Interesting recent results of our research in the area includes

the first example of gold-catalyzed domino cyclization-alkynylation2 and a highly efficient and

practical alkynylation method for thiols3 Herein we will present our most recent work in the area

of electrophilic alkynylation as well as the extension of the use of cyclic hypervalent iodine

reagents to other functionalization reactions

References

1 JP Brand J Waser Chem Soc Rev 2012 41 4165-4179

2 Y Li J P Brand J Waser Angew Chem Int Ed 2013 52 6743-6747

3 R Frei J Waser J Am Chem Soc 2013 135 9620-9623

37

IL14

THEORY AND COMPUTATION PROVIDE INSIGHTS AND DISCOVERY

ON CHEMICAL REACTIONS OF COMPLEX MOLECULAR SYSTEMS

K Morokuma12

1 - Fukui Institute for Fundamental Chemistry Kyoto University Kyoto Japan

2 - Cherry L Emerson Center for Scientific Computation and Department of Chemistry Emory

University Atlanta GA USA

The chemical reaction that creates destroys reorganizes chemical bonds to produce new

compounds is the most important subject of chemistry Theoreticalcomputational studies have

come a long way and are now playing the central role in providing insights in understanding the

mechanism and dynamics of chemical reactions as well as in discovery of new reaction mechanisms

and reaction systems The theory can study not only the reaction of the ground state of molecules in

gas phase but also reactions of excited electronic states as well complicated reactions of complex

molecular systems The information theoreticalcomputational studies can provide is often

complementary to the information experimental studies provide and research on chemical reactions

is becoming impossible without strong collaboration between theorists and experimentalists

In the present talk I will discuss some of our recent studies of chemical reactions We have

developed the Global Reaction Route Mapping (GRRM) strategy for automatic exploration of

reaction pathways of complex molecular systems The ADDF (anharmonic downward distortion

following) and the AFIR (artificial force induced reaction) methods in the GRRM strategy have

been used for determination of not only energy minima and saddle points on the potential energy

hypersurfaces but also minima and saddle points on the conical intersection and crossing seam

hypersurfaces I will discuss the GRRM strategy and applications to several reaction systems

including photodissociation reactions catalytic reactions and enzymatic reactions

38

IL15

COMPUTATIONAL INSIGHTS INTO C-H FUNCTIONALIZATION

JUNGLE

D Musaev

Cherry L Emerson Center for Scientific Computation Emory University Atlanta Georgia USA

I will present our integrated and

collaborative approaches to the

Transition metal catalyzed C-H bond

functionalization I will elaborate our

efforts on understanding the transition

metal catalyzed C-H bond alkylation

and amination reactions and analyze

the factors controlling the reactivity of

these reactions and make intriguing

predictions I will discuss our latest

results [1] on the mono-protected amino acid ligands (MPAA) promoted Pd(II)-catalyzed

enantioselective CndashH activation reactions The presented computation allowed us to gain insights

into the mechanisms nature of active species a ligand coordination mode to the Pd(II) and

transition state structure of the CndashH activation step Our findings were supported by experiments

[1] D G Musaev T M Figg and A L Kaledin Chem Soc Rev DOI 101039C3CS60447K

(2014)

PR3

Ar

Pd

I

Ph

CsF

HCsPd

RZ ZR

Pd

ZRZR

ZR

Pd

ZR

Pd

RZ ZR

Pd

ZR

ZR

ZR ZRPd

Active

Inactive

Cs2-I-F assisted

PdNO

N

O

PG

H Ph

H

i-Pr

H

O

-

O

Ligand accelerated

Protecting Group effectBase (Cs)-effectPd-cluster effect

C-H FUNCTIONALIZATION

DIRECT Ar-Ar COUPLING

SELECTIVE RSHRSeH + C C

Pd(II)- PRECATALYST

39

IL16

A NOVEL TRIFLUOROMETHANESULFONYL HYPERVALENT

IODONIUM YLIDE FOR TRIFLUOROMETHYLTHIOLATION

N Shibata

Nagoya Institute of Technology Department of Nanopharmaceutical Sciences Nagoya Japan

In the last few decades numerous methods for the introduction of a trifluoromethylthio group into

organic compounds have been developed The main strategies are indirect methods including

halogen-fluorine exchange and trifluoromethylation of sulfur-containing compounds such as

disulfides thiols and thiolates Obviously the most attractive and ideal route to constitute the CF3S

moiety is the direct introduction of this functional group However in this approach some

limitations are usually encountered including the use of gaseous and highly toxic reagents such as

CF3SCl or unstable reagents and the modest scope of substrates Although several transition

metal-mediated or catalyzed trifluoromethylthiolation methods have been developed the substrates

are mostly limited to aromatic compounds Recently Billard and co-workers reported that

trifluoromethanesulfanylamides were effective for trifluoromethylthiolation of alkenes alkynes

indoles and organometallic species More recently Lu and Shen also developed a novel hypervalent

iodine reagent for the trifuoromethylthiolation of aryl and vinyl boronic derivatives alkynes and β-

ketoesters Even though these direct trifluoromethylthiolation reagents are shelf-stable a more

critical issue is the fact that these CF3S regents should be prepared in advance by

trifluoromethylthiolations or related trifluoromethylations Due to these limitations and negative

aspects it is thus still necessary to develop an efficient and easily available reagent to introduce the

CF3S moiety directly In contrast to the CF3S unit a trifluoromethanesulfonyl (CF3SO2) unit is

stable and often found in commonly used organic reagents such as CF3SO2Cl CF3SO2Na CF3SO2H

and (CF3SO2)2 In this context we came up with a novel idea of using ubiquitous CF3SO2

compounds as reagents for introducing the CF3S unit under reductive conditions As a part of our

recent work on the chemistry of trifluoromethanesulfonyl compounds (triflones) we herein disclose

a novel trifluoromethanesulfonyl hypervalent iodonium ylide as a shelf-stable reagent for

electrophilic-type trifluoromethylthiolation A wide variety of nucleophiles are nicely converted

into the corresponding trifluoromethylsulfanyl products by this reagent

Reference Y-D Yang A Azuma E Tokunaga M Yamasaki M Shiro N Shibata J Am

Chem Soc 135 8782 (2013)

40

IL17

CATALYSIS-ASSISTED SIGNAL ENHANCEMENT IN NUCLEAR

MAGNETIC RESONANCE

IV Koptyug

International Tomography Center SB RAS Novosibirsk Russia

When parahydrogen (nuclear spin isomer of H2) is used in catalytic hydrogenations instead of

normal H2 the NMR signals of reaction products and intermediates can be enhanced by 3-4 orders

of magnitude and more owing to the phenomenon of parahydrogen-induced polarization (PHIP)

This possibility has been explored previously in the context of activation of H2 by transition metal

complexes and clusters in solution It has been shown that PHIP can help to detect reaction products

and short-lived intermediates not detectable by conventional NMR As most of the industrial

catalytic processes are heterogeneous it would be desirable to employ PHIP in the NMR studies of

heterogeneous catalysts and catalytic reactions The objective of our research is thus to extend the

scope of PHIP applications to the heterogeneously (HET) catalyzed hydrogenation reactions and to

develop a hypersensitive NMR-based technique for the in situ and operando studies of

heterogeneous catalytic processes In addition HET-PHIP can be employed to produce catalyst-free

hyperpolarized liquids and gases for novel MRI applications including the advanced in vivo studies

We demonstrate that similar to their homogeneous counterparts heterogenized transition metal

complexes are able to produce strong NMR signal enhancements when parahydrogen is used in the

hydrogenation reactions [1] Our recent results show that various immobilized metal complexes are

can produce HET-PHIP both in liquid phase and in gas phase hydrogenations In contrast for

supported metal catalysts (eg PtAl2O3) dissociative hydrogen chemisorption and rapid migration

of H atoms on the metal surface were expected to make the required pairwise hydrogen addition to

a substrate molecule impossible Nevertheless we have shown that PHIP can be successfully

observed both in liquid-solid and in gas-solid heterogeneous hydrogenations catalyzed by supported

metal catalysts [1] The NMR signal enhancement was found to be sensitive to the metal

nanoparticle size and shape the nature of the metal and support and the type of substrate used in

the reaction Recently HET-PHIP effects were also demonstrated for several metal oxides and bulk

unsupported metals used as hydrogenation catalysts [2] The implications of these results for the

mechanisms of heterogeneous hydrogenation processes are discussed [13] Further potential

extensions of the technique will be presented including the use of metal-free catalysts for activating

parahydrogen [4] and the prospects of using nuclear spin isomers of molecules other than H2 to

further extend the range of reactions and processes that can be explored in detail using the PHIP

technique [5] In addition to applying HET-PHIP to the mechanistic and kinetic studies of

heterogeneous hydrogenations several MRI applications of HET-PHIP have been already

demonstrated including MR imaging of a catalytic reaction in an operating model microreactor [6]

1 KV Kovtunov VV Zhivonitko IV Skovpin DA Barskiy IV Koptyug Top Curr Chem 338 123

(2013)

2 KV Kovtunov DA Barskiy OG Salnikov AK Khudorozhkov VI Bukhtiyarov IP Prosvirin IV

Koptyug Chem Commun 50 875 (2014)

3 OG Salnikov KV Kovtunov DA Barskiy AK Khudorozhkov EA Inozemtseva IP Prosvirin VI

Bukhtiyarov IV Koptyug ACS Catal 4 2022 (2014)

4 VV Zhivonitko V-V Telkki K Chernichenko TJ Repo M Leskela V Sumerin IV Koptyug J

Amer Chem Soc 136 598 (2014)

5 VV Zhivonitko KV Kovtunov PL Chapovsky IV Koptyug Angew Chem Int Ed 52 13251

(2013)

6 VV Zhivonitko V-V Telkki IV Koptyug Angew Chem Int Ed 51 8054 (2012)

41

IL18

-BOND ACTIVATION REACTION BY TRANSITION METAL AND MAIN-

GROUP ELEMENT COMPOUNDS AND CATALYTIC REACTION

INCLUDING IT

S Sakaki

Fukui Institute for Fundamental Chemistry Kyoto University Takano Sakyo-ku Kyoto 606-8103

Japan

The -bond activation by transition metal complexes attracts a lot of interests in theoretical and

organometallic chemistries because it is crucial in many catalytic reactions by transition metal

complexes In our understanding -bond activation is classified to two categories the concerted

oxidative addition to M (metal) the stepwise oxidative addition via nucleophilic attack the

oxidative addition to M-L (L = neutral ligand) and the heterolytic activation by M-X (X = anionic

ligand) activation by metal center only and that by the metal-ligand moiety12

MLn + R1-R2 cis-MLn(R1)(R

2) (1)

MLn + R1-X [MLn(R1)] --(X) trans-MX(R

1)Ln (2)

MLLn + R1-R2 MLn(R1)(L-R

2) (3)

MXLn + R1-R2 MLn(R1) + R

2-X (4)

We theoretically investigated these reactions and elucidated the characteristic electronic processes

and clear understanding2 We also theoretically investigated catalytic reactions including -bond

activation In this talk we wish to present our recent theoretical studies of carboxylation of

phenylchloride catalysed by a nickel(0) complex hydrosilylation of carbon dioxide catalyzed by

germanium(II)- and zinc(II)-hydride compounds3

In my talk I wish to present comprehensive understanding of these -bond activation reactions and

the importance of -bond activation reaction in such catalytic reactions as CO2 conversion and

cross-coupling reactions

References

1 S Sakaki Y-y Ohnishi H Sato Chem Record 10 29 (2010) W Guan F B Saeed S

Sakaki Inorg Chem in press

2 N Ochi Y Nakao H Sato S Sakaki J Am Chem Soc 129 8615 (2007) N Ochi Y Nakao

H Sato S Sakaki J Phys Chem A 114 659 (2010)

3 N Takagi and S Sakaki J Am Chem Soc 135 8955 (2013) M Deschmukh to be submitted

42

IL19

NONPLANAR HETEROAROMATICS SYNTHESIS AND SELF-ASSEMBLY

M Stepien

Wydziaі Chemii Uniwersytet Wrocіawski

Even though π-electron aromaticity is typically associated with planar structures several classes of

distorted π-aromatics are known including a variety of twisted helical bowl-shaped or tubular

systems Such distortions are of fundamental interest because they provide a means of testing

different aspects of aromaticity theory but they also may have practical consequences as a

potential method of fine-tuning the electronic structure and self-assembly properties of aromatic

compounds

In this contribution two synthetic approaches to nonplanar heteroaromatics will be discussed One

is based on oxidative coupling reactions of pyrrole-containing precursors and is exemplified by our

recent syntheses of peripherally fused porphyrin derivatives1 (1 and 2) and bipyrroles

2 Compounds

1ndash2 are characterized by bathochromically shifted electronic absorptions and very high extinction

coefficients Phenanthroporphyrins 1 and their complexes reveal substitution-dependent aggregation

in solution and form columnar mesophases in the condensed phase The zinc(II) complex of

benzochrysenoporphyrin 2 was found to form a unique 3D-ordered mesophase containing discrete

multiporphyrin aggregates

The other approach to nonplanar aromatics explored in our laboratory which is suitable to the

synthesis of bowl- or belt-shaped structures involves the so-called fold-in synthesis3 performed on

appropriately designed macrocyclic precursors The fold-in concept can be realized using different

reactivity types including Ullmann-type reductive coupling as in the recent synthesis of

chrysaorole (3)34

and FriedelndashCrafts alkylation5

(1) Myśliwiec D Donnio B Chmielewski P J Heinrich B Stępień M J Am Chem Soc

2012 134 4822ndash4833

(2) Gońka E Myśliwiec D Lis T Chmielewski P J Stępień M J Org Chem 2013 78

1260ndash1265

(3) Stępień M Synlett 2013 24 1316ndash1321

(4) Myśliwiec D Stępień M Angew Chem Int Ed 2013 52 1713ndash1717

(5) Kondratowicz M Myśliwiec D Lis T Stępień M in preparation

43

IL20

RHODIUM N-HETEROCYCLIC CARBENE COMPLEXES AS EFFICIENT

CATALYSTS FOR X-H ADDITIONS TO ALKYNES THE QUEST FOR

SELECTIVITY

R Castarlenas A Di Giuseppe L Rubio-Perez L Palacios R Azpiroz V Polo JJ Perez-

Torrente LA Oro

ISQCH Universidad de Zaraaragoza-CSIC

The development of new catalytic systems for the synthesis of added-value products in a selective

manner and with high atom economy is nowadays an important task In this context our group has

recently prepared new rhodium complexes bearing an N-heterocyclic carbene (NHC) ligand that

have been disclosed to be very active and gem-selective for X-H additions across C-C triple

bonds1-4

Experimental and theoretical (DFT) mechanistic studies indicate that the presence of a

bulky powerful electron-releasing NHC and the rational choice of the auxiliary ligands is essential

in order to control the selectivity towards the formation of Markonikov-type products

1 A Di Giuseppe R Castarlenas JJ Perez-Torrente M Crucianelli V Polo R Sancho FJ

Lahoz LA Oro J Am Chem Soc 2012 134 8171

2 L Palacios MJ Artigas V Polo FJ Lahoz R Castarlenas JJ Perez-Torrente LA Oro ACS

Catal 2013 3 2910

3 L Rubio-Peacuterez R Azpiacuteroz A Di Giuseppe V Polo R Castarlenas JJ Perez-Torrente LA

Oro Chem Eur J 2013 19 15304

4 R Azpiacuteroz A Di Giuseppe R Castarlenas JJ Perez-Torrente LA Oro Chem Eur J 2013

19 3812

44

IL21

CATALYTIC OLEFINATION REACTION ndash UNIVERSAL METHOD FOR

SYNTHESIS OF ALKENES

VG Nenajdenko

Moscow State University Department of Chemistry Leninskie Gory Moscow 119992

Catalytic olefination reaction represents new approach to the preparation of double C=C bond N-

unsubstituted hydrazones can be converted into alkenes by treatment with polyhalogenated alkanes

in presence of a base and catalytic amounts of copper salts The reaction has a wide synthetic scope

allowing to prepare both alkyl and aryl halogenoalkenes including fluorinated ones and derivatives

with functional groups Simple experimental procedure which does not require using of

organometallic or toxic organophospourous compounds affordable price and availability of starting

materials high yields and stereoselectivity are distinct advantages of the reaction

R2

R1

COOR

Cl

R2

R1

Cl

CN

R2

R1

F

F

O

R2

R1

R2

R1

Cl

Cl

R2

R1

Br

Br

R2

R1

CH2OH

Cl

R2

R1

CClF2

F

R2

R1

CF3

Cl

R2

R1

Cl

F

R2

R1

CBrF2

F

CBrF2R

R2

R1

CBrF2

F

F

R2

R1

CONR2

Cl

R2

R1

Cl

O

O

R2

R1

I

H

R2

R1

Cl

H

R2

R1

Br

H

45

IL22

HOW TO MAKE COMPLEX MOLECULES FROM SIMPLE STARTING

MATERIAL THE PALLADIUM A POWERFUL TOOL

J Suffert

University of StrasbourgCNRS

In addition to molecular complexity the challenge of the chemist today is also the quest for

efficiency of the synthetic route and maximization of structural complexity Our laboratory

investigations focus for several years on the study of an unprecedented cascade reaction involving a

rare 4-exo-dig cyclocarbopalladation followed by a terminated cross-coupling with an

organometallic reagent A 6 - or 8 -electrocyclization can occur leading to new tricyclic structures

The seminar will show that we can offer an easy access to complex polycyclic molecules resulting

from readily available simple starting materials Eventually it will be possible to propose the

elaboration of a large collection of unprecedented structurally novel molecules based on recent

promising results Below are represented several complex structures that has been prepared through

the powerful 4-exo-dig cyclocarbopalladation Many other extension of this method have not been

so far explored and can afford a multitude of new and original scaffolds

46

IL23

SYNTHESIS OF TIN AND LEAD ANALOGS OF CYCLOPENTADIENYL

ANION AND THEIR APPLICATION TO TRANSITION-METAL

COMPLEXES

M Saito

Department of Chemistry Graduate School of Science and Engineering Saitama University

Shimo-okubo Sakura-ku Saitama-city Saitama 338-8570 Japan

We succeeded in the generation of tetraphenyldilithiostannole 1a[1]

and its considerable aromatic

character was established by X-ray diffraction analysis and theoretical calculations[2]

The lead

analog tetraphenyldilithioplumbole 2 was also found to be aromatic indicating that the concept of

aromaticity is expanded to lead-bearing carbon cycles[3]

After the synthesis of heavier congeners of Cp anion attention was next paid to the preparation of

transition-metal complexes with such heavier Cp ligands The first heavier metallocene was a

ruthenocene bearing a germole ligand[4]

and transition-metal complexes with silole and germole

ligands have already been synthesized The straightforward method for the synthesis of such

metallocenes is the reactions of metallole anions and dianions with transition-metal reagents

However the reactions using stannole anions and dianions had never been reported until recently

We examined the reaction of tetraphenyldilithiostannole 1b[5]

with [CpRuCl]4 and butterfly

complex 3 was obtained instead of an expected ruthenocene[6]

The reaction of 1b with Cp2TiCl2

afforded three-membered ring compound 4 with unique electronic states[7]

The synthesis of the first

neutral triple-decker complex 5 with group 14 metallole ligands was also achieved using silyl-

substituted dilithiostannole 1c

M

R2

R2

R1

R1

L i

L i

M = S n R1

= R2

= P h

M = S n R1

= R2

= E t

M = S n R1

= M e 3S i R2

= P h

M = P b R1

= R2

= P h

1 a

1b

1c

2

R u

R u

S n S n

E tE t

E t

E t

E t

E t

E t

E t

C p

C p

3

T i

S n

S nC p

C p

4

S n

S iM e 3

M e 3S i

P h

P h

R u C p C p R u

5

References

[1] Saito M Haga R Yoshioka M Chem Commun 2002 1002

[2] Saito M Haga R Yoshioka M Ishimura K Nagase S Angew Chem Int Ed 2005 44

6553

[3] Saito M Sakaguchi M Tajima T Ishimura K Nagase S Hada M Science 2010 328

339

[4] Freeman W P Tilley T D Rheingold A L Ostrander R L Angew Chem Int Ed Engl

1993 32 1744

[5] Saito M Kuwabara T Kambayashi C Yoshioka M Ishimura K Nagase S Chem Lett

2010 39 700

[6] Kuwabara T Saito M Guo J D Nagase S Inorg Chem 2013 52 3585

[7] Kuwabara T Guo J D Nagase S Saito M Angew Chem Int Ed 2014 53 434

47

IL24

NEW METHODS FOR PEROXIDE SYNTHESIS

AO Terentev

ZIOCh Moscow Russia

In the last decades organic peroxides have received considerable attention from chemists and drug

design experts which is associated with a need in the search for drugs for the treatment of parasitic

diseases such as malaria and helminth infections Considerable progress has been made in the

design of effective peroxide antimalarial drugs Some synthetic peroxides exhibit activity equal to

or higher than that of artemisinin Peroxides having antitumor or growth-regulatory activity were

also documented In our work we developed new methods for synthesis of various types of

peroxides

It was found that some peroxides posesses pronounced antischistosomal properties and anticancer

activity This work is supported by the Grant of the Russian Foundation for Basic Research (Grant

14-03-00237) and by the Program for Basic Research of the Presidium of the Russian Academy of

Sciences

References

[1] Terentev A Borisov D Yaremenko I Chernyshev V Nikishin G JOrgChem 75 5065-

5071 2010

[2] Terentev A Yaremenko I Chernyshev V Dembitsky V Nikishin G JOrgChem 77

1833-1842 2012

[3] Ingram K Yaremenko IA Krylov I Hofer L Terentev A O Keiser J JMedChem 55

(20) 8700ndash8711 2012

[4] Terentev A O Yaremenko I A Vil V A Dembitsky V M Nikishin G I Synthesis

246-250 2013

[5] Terentev A O Yaremenko I A Vil V A Моisееv I K Konrsquokov S A Dembitsky V

M Levitsky D O Nikishin G I Org Biomol Chem 11 2613ndash2623 2013

[6] IA Yaremenko AO Terentrsquoev VA Vilrsquo RA Novikov VV Chernyshev VA Tafeenko

DO Levitsky F Fleury GI Nikishin Chemistry - A European Journal DOI

101002chem201402594

48

IL25

SYNERGISM BETWEEN THEORY AND EXPERIMENTS IN

ASYMMETRIC CATALYSIS TRANSITION STATE MODELING FOR

RATIONALIZATIONS AND CATALYST DESIGN

RB Sunoj

Department of Chemistry Indian Institute of Technology Bombay Powai Mumbai 400076

Computational quantum chemistry has been increasingly employed toward rationalizing the

stereochemical outcome of a diverse range of reactions1 The approach typically involves the

identification of kinetically significant transition states and intermediates In our laboratory ab

initio as well as DFT methods are employed to gain insights into carbon-carbon and carbon-

heteroatom bond-forming reactions of immediate practical significance2 The key objective is in

establishing the factors responsible for stereoselectivity in such reactions and to employ those

insights toward in silico design of novel catalysts for potential asymmetric applications3

A number of examples wherein the conventional transition state models required systematic

improvements toward accounting the observed product distribution and stereochemical outcome

will be presented In general the presentation would encompass a few contemporary themes in the

domain of organo- and organo-metallic catalysis Interesting interpretationsrationalizations of

experimental observations besides meaningful guidelines for rational improvements in asymmetric

catalysis would remain the key focus of the presentation The contents are designed to cater to a

broad and diverse group of audience hence the chemical insights would receive more emphasis

rather than intricate technical details

[1] (a) Cheong P H ndashY Legault C Y Um J M Celebi-Olcum N Houk K N Chem Rev

2011 111 5042 (b) Sunoj R B Wiley Interdisciplinary Reviews Comput Mol Sci 2011 1

920

[2] (a) Shinisha C B Sunoj R B J Am Chem Soc 2010 132 12135 (b) Sharma A K

Sunoj R B Angew Chem Int Ed 2010 49 9373 (c) Sharma A K Sunoj R B Chem

Commun 2011 47 5759 (d) Jindal G Sunoj R B Chem Eur J 2012 18 7045 (e) Jindal

G Sunoj R B Angew Chem Int Ed 2014 53 4432 (f) Anand M Sunoj R B Schaefer

H F J Am Chem Soc 2014 136 5535

[3] (a) Shinisha C B Sunoj R B Org Biomol Chem 2007 5 1287 (b) Shinisha C B Sunoj

R B Org Lett 2009 11 3242 (c) Jindal G Sunoj R B Org Bimol Chem 2014 12 2745

49

IL26

CATALYTIC ASYMMETRIC CROTYLATION METHOD DEVELOPMENT

AND APPLICATION IN TOTAL SYNTHESIS

AV Malkov PS Orsquohora CA Incerti-Pradillos MA Kabeshov

Loughborough University Loughborough LE11 3TU UK

Secondary metabolites 1-5 isolated from marine soft coral Pseudopterogorgia elisabethae exhibit a

wide range of useful biological properties which include anti-tubercular anti-inflammatory

antimicrobial and analgesic activities [1] The analgesic properties are superior to the existing

industry standards As a result partially purified gorgonian extracts are used in commercial skin

care products for topical applications [2]

H

OH

HO

Pseudopterosin A-Daglycone

H H

O

O

HO

H

OH

O

O

H

O

O

HO

HH

1 2 3 4

(ndash)-Elisapterosin B (ndash)-Colombiasin A(+)-Elisabethadione(+)-Erogorgiaene

5

Herein we present a novel general strategy for a scalable enantioselective total synthesis of

serrulatane diterpenes 1 and 2 Synthetically a major challenge associated with the synthesis of

these compounds is the control of the three stereocentres in the absence of directing functional

groups Our principal strategy is based on the asymmetric crotylation of cinnamyl-type aldehyde 10

with Z-crotyltrichlorosilane 9 to produce homoallylic alcohol 8 with a set of stereogenic centers that

will be used to control the stereochemistry of oxy-Cope rearrangement (8 rarr 7) and the subsequent

transformations towards the advanced intermediate 6 Development of novel efficient Lewis base

catalysts for the asymmetric crotylation and completion of the total synthesis of (ndash)-elisabethadione

and (ndash)-erogorgiaene will be discussed in detail

SiCl3O

OH

Cat

H

O

Anionic oxy-Cope

H

OH6

cationic cyclisation

Wittigolefination

12

7

810

Rn

Rn

RnRn

1

4

11

9

References

[1] A D Rodriguez C Ramirez J Nat Prod 2001 64 100-102

[2] A Kijjoa P Sawanwong Mar Drugs 2004 2 72-82

50

IL27

SYNTHESES OF METAL COMPLEXES WITH TRANS-CYCLOALKANE-

12-DIYL-[OSSO]-TYPE BIS(PHENOLATE) LIGAND AND ISOSPECIFIC

POLYMERIZATION OF ALPHA-OLEFINS

A Ishii

Department of Chemistry Graduate School of Science and Engineering Saitama University

Shimo-okubo Sakura-ku Saitama 338-8570 Japan

Efficiency and stereoselectivity of reactions catalyzed by metal complexes are often greatly affected

by auxiliary ligands of the catalysts We have recently developed tetradentate auxiliary ligands 1

featuring oxygen and sulfur coordination sites and fusion of trans-cycloalkane-12-diyl rings1ndash3

The

[OSSO]-bis(phenolate) ligand 1 (n = 3) was applied to the synthesis of zirconium complex 2 and we

found that a combination of 2 and an activator catalyzes the polymerization of 1-hexene with high

activity and high isospecificity1 in comparison with previously reported group 4 metal complexes

bearing [OSSO]-type ligands4 We have also synthesized Ti

5 Zr

6 Hf

7 V

8 Nb

8 Ta

8 and Al

9

complexes with 1 (n = 3) and investigated catalytic reactions with these complexes In this paper

we report the syntheses and structures of these metal complexes and their catalytic ability with

recent progress

S

SO

tBu

tBu

O

tBu

tBu

ZrCH2Ph

CH2Ph

1 2

S OH

tBu

tBu

OH

tBu

tBu

Sn

Bu 2(Ph3C)[B(C6F5)4] Bu Bu Bu Bu Bu

isotactic poly(1-hexene) ([mmmm] gt95)

activity =

2500 gbullmmolndash1bullhndash1

Mw = 59000 PDI = 17

References

1 Ishii A Toda T Nakata N Matsuo T J Am Chem Soc 2009 131 13566ndash13567

2 Ishii A Toda T Nakata N Matsuo T Phosphorus Sulfur Silicon 2011 186 1169ndash1174

3 Ishii A Asajima K Toda T Nakata N Organometallics 2011 30 2947ndash2956

4 Nakata N Toda T Ishii A Polym Chem 2011 2 1597ndash1610

5 Nakata N Toda T Matsuo T Ishii A Inorg Chem 2012 51 274ndash281

6 Toda T Nakata N Matsuo T Ishii A J Organomet Chem 2011 696 1258ndash1261

7 Nakata N Toda T Matsuo T Ishii A Macromolecules 2013 46 6758ndash6764 Nakata N

Saito Y Watanabe T Ishii A Top Catal 2014 57 918ndash922

8 Toda T Nakata N Matsuo M Ishii A ACS Catal 2013 3 1764minus1767

9 Nakata N Saito Y Ishii A Organometallics 2014 33 1840ndash1844

51

IL28

NEW APPROACH FOR THE SYNTHESIS OF COMPOUNDS CONTAINING

CF2 FRAGMENT

AD Dilman VV Levin AA Zemtsov MD Kosobokov

N D Zelinsky Institute of Organic Chemistry

Existing methods for the synthesis of compounds containing CF2 fragment either employ hazardous

reagents or require long synthetic sequence We propose a new approach towards difluorinated

compounds based on the coupling of three components mdash nucleophile difluorocarbene and

electrophile

As nucleophiles organometallic reagents can be employed The insertion of difluorocarbene into

carbon-zinc bond of organozinc reagents leads to new organozinc species which can be quenched

by halogen or proton1 or coupled with allylic electrophiles

2

The interaction of trimethylsilyl cyanide with difluorocarbene affords difluoro(trimethylsilyl)-

acetonitrile This reagent was used in reactions with aldehydes and imines furnishing fluorinated

alcohols and amines3 The addition products can be transformed into a variety of heterocyclic

molecules4

This work was supported by the Ministry of Science (project MD-475020133) and Russian

Foundation for Basic Research (projects 13-03-12074 14-03-00293 14-03-31253_mol_a 14-03-

31265_mol_a)

1 Levin V V Zemtsov A A Struchkova M I Dilman A D Org Lett 2013 15 917ndash919

2 Zemtsov A A Kondratyev N S Levin V V Struchkova M I Dilman A D J Org

Chem 2014 79 818ndash822

3 Kosobokov M D Dilman A D Levin V V Struchkova M I J Org Chem 2012 77

5850ndash5855

4 Kosobokov M D Struchkova M I Arkhipov D E Korlyukov A A Dilman A D

J Fluorine Chem 2013 154 73ndash79

52

IL29

TOWARDS REALISTIC FIRST-PRINCIPLES MODELLING OF

COMPLEXITY IN HETEROGENEOUS CATALYSIS

KM Neyman

ICREA and Universitat de Barcelona

Active components present in heterogeneous catalysts as nano-aggregates of thousands atoms

remain inaccessible for the first-principles (based on DFT) computations due to their size and

complexity However such species could be rather realistically represented by computationally

tractable smaller model nanoparticles (NPs) whose surface sites only marginally change the

reactivity with increasing particle size We illustrate this for decomposition of methane1 and

methanol2-4

on Pt and Pd catalysts as well as building of active sites on Ptceria catalysts56

We

show that using common slab models and thus neglecting the nanoscopic effects in these and

similar systems could lead to severe misrepresentation of the surface reactivity7

Methane decomposition on Pt NP is calculated to be more exothermic than on Pt(111) surface and

proceed via much lower activation barriers for the rate-limiting steps1 The reason for Pt activation

by nanostructuring is that CHx species are stabilized on NP edges converting the first two steps of

CH4 decomposition from endothermic on Pt(111) to exothermic on Pt79 The higher activity of edge

Pt atoms was assigned to their lower coordination and higher flexibility

The flexibility affects not only adsorption properties of sites with low-coordinated atoms but also

nearby terrace sites This effect is most pronounced for strongly bound adsorbates eg atomic C It

is a common by-product in decomposition reactions on Pd2 able to modify catalyst properties upon

exothermic migration subsurface34

The most spectacular effect of flexibility of Pd NPs is on the

subsurface migration barriers of surface C Near NPs edges these barriers essentially vanish

Presence of subsurface C makes Pd NPs more transparent for subsurface diffusion of adsorbed

hydrogen3 which in turn enables sustainable hydrogenation of olefins on Pd catalysts

Strong metal-support interactions can radically modify surface chemistry Due to catalysts

complexity the microscopic origin of such effects is usually unresolved However our study on

models of Pt-ceria catalysts succeeded to uncover atomic details of interactions in this system5

Calculations identified two types of oxidative Pt-ceria interactions electron transfer from a Pt

particle to the support and O transport from ceria to Pt The former is favorable on ceria supports

regardless their morphology But the O transfer requires the presence of Pt in close contact with

nanostructured ceria being inherently a nano-effect Both effects were detected by monitoring the

Ce3+

Ce4+

ratio using resonant photoelectron spectroscopy on Pt-CeO2 model catalysts

These case studies reveal very significant differences in the surface reactivity derived from

customary slab-model calculations and those employing dedicated NP models The latter expose a

variety of active sites whose structure and geometric flexibility notably better match those of the

sites present under experimental conditions Thus we advocate much broader usage of suitable NP

models in ldquocatalysis from first principlesrdquo 1 F Vintildees Y Lykhach T Staudt M P A Lorenz C Papp H-P Steinruumlck J Libuda K M Neyman A Goumlrling -

Chem Eur J 2010 16 6530

2 I V Yudanov A V Matveev K M Neyman N Roumlsch - J Am Chem Soc 2008 130 9342

3 K M Neyman S Schauermann - Angew Chemie Int Ed 2010 49 4743

4 H A Aleksandrov F Vintildees W Ludwig S Schauermann K M Neyman - Chem - Eur J 2013 19 1335

5 G N Vayssilov Y Lykhach A Migani T Staudt G P Petrova N Tsud T Skaacutela A Bruix F Illas K C Prince

V Matoliacuten K M Neyman J Libuda - Nature Mater 2011 10 310

6 A Bruix Y Lykhach I Matoliacutenovaacute A Neitzel K C Prince V Potin F Illas V Matoliacuten J Libuda K M

Neyman et al - Angew Chemie Int Ed 2014 53 doi 101002anie201402432

7 S M Kozlov K M Neyman - Top Catal 2013 56 86

53

IL30

С-С TRIPLE BOND ACTIVATION BY PLATINUM METALS UNDER

HOMO- AND HETEROGENEOUS CONDITIONS DESIGN OF NEW

CATALYTIC REACTIONS

SA Mitchenko

LM Litvinenko Institute of Physical Organic and Coal Chemistry National Academy of Sciences

of Ukraine Donetsk Ukraine

Petroleum and natural gas are the main sources of raw materials for modern bulk and fine chemical

industry Since the middle of the last century this changed the industry redirecting technology

previously based on acetylene towards olefinic stuff and synthesis gas Nevertheless series of large-

scale (for example manufacture of vinyl ethers pyrrolidone and N-methylpyrrolidone butanediol

etc) and fine (drugs and fragrances crop protecting agents etc) chemical production based on

acetylene hydrocarbons possesses definite advantages and is still developing Besides acetylene

hydrocarbons are inevitably formed as by-products in oil processing yielding olefins and taking

into account the modern industrial scales and prices of starting materials these by-products should

be efficiently utilized On the other hand coal and natural gas supply as against of petroleum allow

us to regard them as practically inexhaustible source of acetylene Increasing interest to the catalytic

chemistry of acetylene (see for example [1 2]) can be motivated in particular by these

considerations

Results of development of new catalytic transformations of acetylene under homo- and

heterogeneous conditions will be presented and discussed

References

1 Alonso F Beletskaya IP Yus M Chem Rev 2004 104 3079

2 Ananikov V P Beletskaya I P Organometallics 2012 31 1595

54

IL31

SYNERGISTIC EFFECTS IN DESIGNING COMBINED CATALYTIC

SYSTEMS (COMBICATrsquoS) FOR ABATEMENT OF

NITROGEN OXIDES (NOX)

AYu Stakheev

Zelinsky Institiute of Organic Chemistry Catalysis division Moscow Russia

Anthropogenic emission on nitrogen oxides (NOx = NO NO2 N2O) becomes an important issue

since the amount of anthropogenic NOx nowadays exceeds biogenic emission (~110 Mt vs 80

Mtannual) and their impact on environment is significant The most effective method for

abatement of nitrogen oxides is their selective catalytic reduction (SCR) by urea or NH3

2NO + 2NH3 + 12O2 = 2N2 + 3 H2O

However activity of the traditional NH3-SCR catalysts at the temperatures below 250oC is not

sufficient due to the stringent restrictions imposed by environmental legislations on NOx emission

from mobile sources The effective solution can be provided by Cu-containing zeolite catalyst

however high cost often limits their practical application Our recent study revealed alternative

approach and indicated that promising NH3-DeNOx activity at Treact lt 250degC CAN BE ATTAINED OVER

combined catalysts (CombiCat) comprising zeolite component (possessing high activity in SCR)

and a redox component (having high activity in NO oxidation) For such compositions we found a

pronounced synergistic effect and the catalytic activity of the COMBICATrsquoS significantly exceeds

activity of the individual components A number of compositions have been tested for searching

synergistic effects and the most remarkable results have been observed for [CuAl2O3 +FeBETA]

[MnAl2O3 + FeBETA [CeZr +FeBETA] [MnCeZr + FeBETA] MnFeBETA Interestingly that

the studied composition exhibits favorable performance in selective oxidation of NH3

2NH3 + 32 O2 = N2 + 3H2O

Therefore CombiCatrsquos are capable to accomplish two functions SCR catalyst and removal of

residual NH3 In addition to that for the compositions comprising CeO2-ZrO2 component a

promising soot oxidation activity has been observed

Detailed study of a possible origin of the observed synergistic effects suggests that the improvement

of NH3-DeNOx activity can be attributed to a ldquodual functionrdquo reaction mechanism comprising two

main stages

(1) NO + O2 harr NO2 over redox component

(2) NO + NO2 + 2NH3 rarr N2 + 3H2O over zeolite component

However further research is required for revealing overall reaction network and understanding

reaction mechanism responsible for observed synergy

55

IL32

NOVEL COLCHICINOIDS AS POTENTIAL ANTITUMOR AGENTS

A Yu Fedorov

Department of Organic Chemistry Nizhny Novgorod State University Gagarina av 23 Nizhny

Novgorod 603950 Russian Federation

A range of indole - and furane-containing allocolchicinoids was synthesized

Several from synthesized compounds manifested high in vitro and in vivo antitumor activity

Acknowledgment

We thank the Russian Foundation for Basic Research (projects 14-03-91342 and 12-03-00214-a)

The Ministry of Education and Science of The Russian Federation (project 46192014K) The

research is partly supported by the grant 02В49210003 of The Ministry of Education and

Science of the Russian Federation to Lobachevsky State University of Nizhni Novgorod

56

IL33

ENANTIOSELECTIVE CATALYSIS BY CHIRAL BROslashNSTED ACIDS AND

CHIRAL BRШNSTED BASES

M Terada

Tohoku Univsersity Department of Chemistry Sendai Japan

Chiral phosphoric acids 1 have become one of the most versatile types of chiral Broslashnsted acid

catalysts identified to date and have been applied to a broad range of enantioselective

transformations12)

In my continuing efforts to broaden the scope of enantioselective catalysis by 1

activation of oxygenated functional groups other than imines and related functional groups is our

recent research interest To expand the scope of chiral Broslashnsted acid catalysis recently a novel

chiral bis-phosphoric acid 2 was developed as a highly active and efficient enantioselective

catalyst3)

On the other hand intense interest has been devoted to the development of chiral

uncharged organosuperbase catalysts during the past decade In an effort to develop efficient chiral

organobase catalysts we designed and synthesized unique axially chiral Broslashnsted base 34)

3

functioned as the efficient enantioselective catalysts for the activation of pro-nucleophile having a

relatively acidic proton such as 13-dicarbonyl compounds To expand the scope of chiral Broslashnsted

Base catalysis development of much stronger organosuperbase is highly demanded We hence

designed a pseudo C2-symmetric bis(guanidino)iminophosphorane 4 as a novel family of chiral

organosuperbases5)

In my presentation I briefly introduce these chiral Broslashnsted acid catalysts (1

and 2) and base catalysts (3 and 4) In particular I would like to present a novel chiral Broslashnsted

base catalyst 4 in details

References

1) (a) Terada M Synthesis 2010 1929-1982 (b) Terada M Chem Commun 2008 4097-4112

2) Uraguchi D Terada M J Am Chem Soc 2004 126 5356-5357

3) Momiyama N Konno T Furiya T Iwamoto T Terada M J Am Chem Soc 2011 133

19294-19297

4) Terada M Ube H Yaguchi Y J Am Chem Soc 2006 128 1454-1455

5) Takeda T Terada M Y J Am Chem Soc 2013 135 15306-15309

57

IL34

IONIC LIQUIDS WATER AND LIQUID OR SUPERCRITICAL CO2 AS

PERSPECTIVE MEDIA FOR ASYMMETRIC ORGANOCATALYSIS

SG Zlotin

ND Zelinsky Institute of Organic Chemistry Russian Academy of Sciences

Over the last decade amazing results have been associated with the extensive application of

asymmetric organocatalysts in organic synthesis In the presence of small metal-free chiral organic

molecules (α-amino acid or cinchona alkaloid derivatives BINOL phosphoric acids and other

chiral compounds) available prochiral reagents can be easily converted into chiral products of high

molecular complexity in high yields and with excellent enantioselectivities Unlike organometal

catalysts organocatalysts do not contaminate products with toxic heavy metals and this is important

in terms of medicinal chemistry However in some cases they may be responsible for hardly

separable and potentially dangerous organic impurities

To facilitate product purification and recovery of precious chiral catalysts immobilized forms of

organocatalysts tagged to polymers or ionic groups have been designed and organocatalytic

reactions have been carried out in so called ldquoneotericrdquo green solvents particularly in ionic liquids

(IL) water and liquid or supercritical (sc) carbon dioxide In these systems a catalyst and a product

are located in different phases during the catalytic process andor the working-up step

We developed highly efficient enantioselective cross-aldol reactions between various carbonyl

compounds in the presence of proline or prolinamide-derived organocatalysts in the IL andor

aqueous environment An original method for adapting -amino acid-sourced IL-supported chiral

organocatalysts to the aqueous medium via an incorporation of long-chain alkyl groups and

hydrophobic anions into their molecules and by performing asymmetric reactions in reagentswater

two-phase systems was elaborated Corresponding aldol products were obtained in high yields and

with extremely high anti -diastereo- (dr up to 98 2) and enantioselectivities (ee up to 99) under

proposed conditions After product isolation the remaining catalyst-water heterogeneous system

could be reused up to 15 times without a decrease of product yield and selectivity of the reaction1

Carbon acids in particular malonates malononitrile and anthranone appeared to react

enantioselectively with nitroalkenes in the presence of tertiary aminethiourea-derived bifunctional

organocatalyst in liquid CO2 as a green substitute of toxic organic solvents to afford the respective

Michael adducts in moderate to high yields and with enantioselectivities of up to 92 ee2 The first

ldquogreenrdquo asymmetric organocatalytic reaction in sc-CO2 namely a bifunctional squaramide-

catalyzed addition of diphenylphosphite to α-nitroalkenes to afford β-nitrophosphonates in high

yields and with ee-values of up to 94 was elaborated3 In this way the most active (R)-enantiomer

of the therapeutically useful GABAB receptor agonist baclofen a key precursor of the chiral

anticonvulsant pregabalin and both enantiomers of pharmacologically important β-amino

phosphonic acid derivatives were synthesized A significant potential of the supercritical extraction

for product isolation and catalyst recovery which completely eliminates the use of organic solvents

during the working-up procedure was demonstrated

The work was financially supported by the Russian Foundation of Basic Research (projects 12-03-

00420 14-03-31321 and 14-03-92701)

1 DE Siyutkin AS Kucherenko SG Zlotin In ldquoComprehensive Enantioselective

Organocatalysis Catalysts Reactions and Applicationsrdquo ed by PI Dalco Wiley-VCH 2013

v 2 p 617-650

2 AG Nigmatov IV Kuchurov DE Siyutkin SG Zlotin Tetrahedron Lett 2012 53 3502

3 IV Kuchurov AG Nigmatov EV Kryuchkova AA Kostenko AS Kucherenko SG

Zlotin Green Chem 2014 16 1521

58

IL35

MAKING OLEFIN METATHESIS WORK - RECENT RESULTS IN

RUTHENIUM CATALYSTS DESIGN

KL Grela

Biological and Chemical Research Centre Faculty of Chemistry University of Warsaw

Ruthenium-catalyzed olefin metathesis reactions represent an attractive and powerful

transformation for the formation of new carbon-carbon double bonds [1] This area is now quite

familiar to most chemists as numerous catalysts are available that enable a plethora of olefin

metathesis reactions [1] However formation of substituted and crowded double bonds decreasing

the amount of metal using metathesis in green context etc still remain a challenge making

industrial applications of this methodology difficult [2] These limitations can be solved by

designing new more active and stable catalysts and catalysts that can be easier removed recycled

[3]

During the lecture a number of representative examples will be presented

Artwork copy Katarzyna Felchnerowska wwwfbcomeffefineart

References

[1] Olefin Metathesis Theory and Practice Grela K (Ed) John Wiley amp Sons 2014

[2] Thayer A Chemical amp Engineering News 2007 85 (07) 37

[3] Clavier H Grela K Kirschning A Mauduit M Nolan S P Angew Chem Int Ed 2007

46 6786-6801

59

60

Oral Communications

61

62

OC1

THE FIRST CYCLOPENTADIENYL NICKEL COMPLEXES BEARING A

SILYL GROUP OR HYDROGEN SUBSTITUTED PHOSPHINE

CHELATING SIDECHAIN

I Werner H Butenschoen

Institute of Organic Chemistry Leibniz Universitaet Hannover Hannover Germany

The only known secondary phosphine pendant cyclopentadienyl complexes are those of zirconium

and hafnium reported by Ishiyama et al in 2002[1]

Since these complexes contain a reactive

phosphorus-hydrogen bond they were converted into the corresponding phosphide-substituted

cyclopentadienyl chelate complexes[2]

Both systems were successfully applied in catalytic ethylene

and styrene polymerization reactions as well as in ethylenestyrene copolymerization reactions[3]

To our knowledge no analogous complexes of late transition metals containing a phosphorus-

hydrogen or a phosphorus-silyl bond have so far been reported We report on the synthesis of the

first cyclopentadienyl nickel complexes 1-4 and 5 7 bearing a silyl group and hydrogen substituted

phosphine chelating sidechain respectively

Treatment of complex 5 with SIMes induced the decomplexation of the secondary phosphane

substituted tether delivering exclusively nickel carbene complex 6

Recrystallization of complex 7 from hexaneethyl acetate (11) at 30 degC afforded crystals suitable

for an X-ray crystal structure analysis

References

[1] T Ishiyama H Nakazawa K Miyoshi J Organomet Chem 2002 648 231

[2] T Ishiyama T Mizuta K Miyoshi H Nakazawa Organometallics 2003 22 1096

[3] T Ishiyama K Miyoshi H Nakazawa J Mol Cat A-Chem 2004 221 41

63

OC2

EXPANDED RING N-HETEROCYCLIC CARBENE TRANSITION METAL

COMPLEXES SYNTHESIS STRUCTURE APPLICATIONS IN

CATALYSIS

MS Nechaev1 AF Asachenko

2 PB Dzhevakov

2 OS Morozov

2 GV Proskurin

1 PS

Gribanov1

1 - Moscow State University Department of Chemistry Moscow Russia

2 - A V Topchiev Institute of Petrochemical Synthesis RAS Moscow Russia

N-heterocyclic carbenes (NHCs) became widely used as organocatalysts and as ligands in transition

metal catalysis Most of NHC-metal complexes known to date are derived from five-membered ring

imidazol-2-ylidene and imidazolin-2-ylidene type carbenes In recent years our group develops

chemistry of 6- 7- and 8-membered ring carbenes Expanded ring carbenes (er-NHCs) exhibit

superior stereoelectronic properties in comparison with five-membered ring counterparts

Expansion of the ring leads to significant increase in donor strength and sterical hindrance

In this contribution we report our recent results on theoretical calculations of electronic structure

and ligand properties of er-NHCs efficient methods of synthesis of precursors and generation of

free carbenes synthesis of late transition metal (Cu Ag Au Pd) complexes It was found that er-

NHC complexes of palladium are highly active in Suzuki-Miyaura coupling in water and

dimerization of terminal alkynes with formation of E-enynes Cationic gold complexes are active

catalysts of addition of nucleophiles to carbon-carbon triple bonds

64

OC3

PALLADIUM-CATALYZED CndashH ALKENYLATION OF ARENES USING

SULFUR-CONTAINING DIRECTING GROUPS A COMPARATIVE STUDY

KV Luzyanin AN Marjanov VP Ananikov

Laboratory of Cluster Catalysis Saint Petersburg State University Universitetsky pr 26 Stary

Petergof 198504 Russia

Direct alkenylation of organic substrates via directing-group assisted functionalization of the CH

bond has emerged as a valuable tool for creation of new sp2-sp

2 bonds In the contrast to the

MirozokindashHeck reaction that starts from the aryl halides this procedure works with inactivated

arenes and is favorable from both economical and environmental points of view Several types of

directing groups have been evaluated in the direct alkenylation up to date eg ketones and

carboxylates amides pyridine sulfoxides and ethers and thioethers Among them functionalization

of sulfur-containing compounds (Scheme 1) ie pyridine thioesters and sulfoxides as well as

structurally related benzylic thioethers (in those sulfur moiety plays a role of a directing group)

attracts rapidly growing attention On the one hand functionalization of such compounds leads to

interesting derivatives containing both alkene and sulfur functions while on the other hand sulfur-

based directing groups in these species can be easily removed after reaction from the resulting

products without compromising other functionalities1ndash3

Scheme 1 Direct alkenylation of arenes using sulfur-containing directing groups

In the current report we summarize data accumulated up to date regarding direct CH-alkenylation

of sulfur-containing organic compounds A particular emphasis is given to the evaluation of the

assistance provided by different sulfur-containing directing groups in comparison to other common

directing moieties known to be employed for this purpose

Acknowledgements This work has been partially supported by the Saint Petersburg State

University (research grant from Laboratory of Cluster Catalysis) and the Russian Fund for Basic

Research (grant 14-03-01005)

References 1 Garciacutea-Rubia A Fernaacutendez-Ibaacutenez M A Goacutemez Arrayaacutes R Carretero J C Chem Eur J

2011 17 3567ndash3570

2 Yu M Xie Y Xie C Zhang Y Org Lett 2012 14 2164ndash2167

3 Zhang X-S Zhu Q-L Zhang Y-F Li Y-B Shi Z-J Chem Eur J 2013 19 11898ndash

11903

65

OC4

IN PURSUIT OF A NOVEL IMIDATE-BASED SALEN-TYPE LIGAND

CLASS

J Van Der Eycken1 P Janssens

1 T Noel

2

1 - Ghent University Department of Organic Chemistry

2 - Eindhoven University of Technology Department of Chemistry and Chemical Engineering

Micro Flow Chemistry amp Process Technology

An increasing ecological awareness and global competitiveness have challenged the chemical

industry towards a higher level of sustainability through innovation and technology In research the

majority of topics on sustainable process development deals with catalysis[1]

Furthermore in

organic synthesis transition metal catalysis already plays a vital role in the synthesis of biologically

active compounds[2]

N N

OH HO

N N

H H H HO O

OH HO

L1 L2

Bisimidate ligand L2 shows striking similarities with Salen ligands (L1) We reasoned that this

could open new opportunities for our already well-established imidate ligand family [3-5]

Nevertheless the applicability of this ligand in the MnV-catalyzed asymmetric epoxidation reaction

turned out to be more complicated than expected

In this communication the search towards an effective novel imidate-based Salen-type ligand class

will be discussed from a ligand design point of view

References

[1] Dichiarante V Ravelli D Albini A Green Chem Lett Rev 2010 3 105

[2] a) Noyori R Angew Chem Int Ed 2002 41 2008 b) Busacca CA Fandrick DR Song

JJ Senanayake CH Adv Synth Catal 2011 353 1825

[3] a) Noeumll T Bert K Van der Eycken E Van der Eycken J Eur J Org Chem 2010 21

4056 b) Bert K Noeumll T Van der Eycken J Org Biomol Chem 2012 10 8539 c) Noeumll T

Bert K Janssens P and Van der Eycken J (2012) ldquoChiral Imidate Ligands Synthesis and

Applications in Asymmetric Catalysisrdquo in Innovative Catalysis in Organic Synthesis

Oxidation Hydrogenation and C-X Bond Forming Reactions (ed P G Andersson) Wiley-

VCH Verlag GmbH amp Co KGaA Weinheim Germany doi 1010029783527646586ch14

66

OC5

NITROALKANES IN PPA AS NEW REAGENTS FOR DIRECT METAL-

FREE AMINATION OF ARENES

AV Aksenov1 NA Aksenov

1 IV Aksenova

1 M Rubin

2 DA Aksenov

1

1 - Department of Chemistry North Caucasus Federal University Stavropol Russian Federation

2 - Department of Chemistry University of KansasLawrence USA

Aromatic amines represent an important class of organic compounds Many of them demonstrate

important biological activities Various multi-step methods for preparation of these compounds

have been developed including electrophilic nitrationreduction sequence Schmidt and Beckmann

rearrangements etc The most appealing methods however are those that allow for direct

introduction of an amino-group to a non-substituted arene over a single step

Direct electrophilic acetamidation of arenes 2 with primary nitroalkanes 1 in polyphosphoric acid

(PPA) recently developed in our laboratories can be viewed as an example of such an approach

R

N+

O

O

P P A

R

N+

O

O P

O

O H

O R

2

R3

R1

R4

R2

N

R

O

PO

O H

O

R3

R4

R1

R2

NH

R

OR3

R1

R4

6 3 -9 2

2

1

3 R=Me Pr Ph Bn R

1 R

2 R

3 R

4=H Me OH MeO CHO

Benzene and arenes with electron-donating substituents can be engaged in this reaction Electron

deficient arenes are inert The process is highly selective the electrophilic attack is always directed

to para-position with respect to a substituent already present in the ring

Anthracene 4 and indole 5 were successfully involved into the acetamidation reaction In reaction of

dibenzo-18-crown-6 ether monoacetamide was formed along with quite a large amount of bis-

acetamination isomeric products

The reaction involving secondary nitroalkanes is also interesting Since the nitroso compound 4

resulting from electrophilic attack to the aromatic ring is not able to isomerize oxime it attacks a

second molecule of arene After rearrangement this leads to the formation of diarylamines 5

N+ O

O P O2H

- H +N

O H

O P O2H

R1

R2

P P A

O

R1

R2

NO

R1

R2

- H2O R

1

R2

N

O HR

1

R2

R1

R2

R1

R2

N

O H

R1

R2

R1

R2

NH

+-P P A

+

4

5 5 5 -6 1 R

1 R

2 =H Me MeO CHO

A novel protocol for direct and regioselective metal-free acetamination and amination of arenes in

reactions with primary and secondary nitroalkanes in polyphosphoric acid media was developed A

new preparative approach to 5-aminoindoles and diarylamines employing this reaction was

demonstrated

This work was carried out with financial support from the Russian Foundation Basic Research

(grants 13-03-00304 a and 14-03-31288 mol_a)

67

OC6

UROTROPINE ISOMER (14610-TETRAAZAADAMANTANE)

MOLECULAR SIMPLICITY AND MOLECULAR COMPLEXITY OF

HETEROADAMANTANE CAGE

AYu Sukhorukov AN Semakin IS Golovanov SL Ioffe VA Tartakovsky

ND Zelinsky Institute of Organic Chemistry Moscow Russia

For more than 100 years heteroadamantanes have been objects of rapt attention for fundamental

and applied chemistry These cage polycyclic systems represent interest not only due to their unique

properties but also as convenient models for the study of basic problems dealing with structure and

reactivity of organic compounds Among many heteroadamantanes 1357-tetraazaadamantane

(urotropine) which was first obtained by A Butlerow in 1859 plays probably the most important

role from an applied point of view Urotropine is widely used in medicine polymer production

food industry as well as organic synthesis coordination chemistry and MOFs design This simplest

Td-symmetrical 1357-tetraazaadamantane is the only known representative of the class of

tetraazaadamantanes In this context the possibility of existence of other tetraazaadamantanes

isomeric to urotropine represents considerable fundamental interest

The present report deals with the first synthesis of 14610-tetraazaadamantane (ldquoisourotropinerdquo)

the C3v-symmetrical structural isomer of urotropine and a series of its derivatives (see Figure) X-

Ray and quantum-chemical studies demonstrate remarkable distinctions in structures of urotropine

and ldquoisourotropinerdquo cages probably arising from different types of lp(Neq) C N interactions in

these heterocage systems Since substitution at bridge and bridgehead nitrogen atoms can be easily

installed 14610-tetraazaadamantane can be considered as a new rigid multivalent (3+1) scaffold

for the design of complex functional molecules and materials

Acknowledgement

The financial support from RFBR (grant 14-03-00933a) and Russian Presidentrsquos Council for Grants

(grant MK-391820133) is greatly acknowledged

68

OC7

PALLADIUM-CATALYZED CROSS-COUPLING REACTION OF

ALCOHOL WITH ARYL CHLORIDE THROUGH C-C BOND ACTIVATION

C-H Jun H-S Park D-S Kim

Yonsei University Department of Chemistry Seoul South Korea

The C-C bond activation is one of challenging subjects in organometallic chemistry1 Especially

catalytic version of C-C bond activation has been recently achieved by chelation assisted transition

metal catalyst consisted of Rh(I) and 2-amino-3-picoline2 During the course of our studies on

these types of C-C bond activation we found decarbonylative esterification of aliphatic alcohol

with aryl chloride by palladium metal as shown below For example when the reaction of

chlorobenzene and 1-naphtylethanol was carried out at 150oC under PdC and NaF base a mixture

of three products 1-naphtylethyl benzoate ester benzene and 1-methylnaphthalene was obtained

in reasonable yields

The reaction mechanism is proposed as follows The reaction proceeds through several consecutive

reactions Initially primary alcohol is oxidized by aryl chloride to aldehyde with formation of aryl-

H under palladium catalyst Aldehyde is decarbonylated by Pd to generate alkane and (CO)Pd The

intermediate (CO)Pd is oxidatively added to aryl chloride to form acyl-PdCl complex which reacts

with alcohol to give ester compounds In this reaction reactivity of substrate should be well

balanced The reactivity of chloroarene is suited for this purpose since other aryl halide such as

bromobenzene and iodobenzene did not show any reactivity in this reaction This result is quite

interesting since aryl chloride is least reactive for common C-C bond coupling reaction while aryl

iodide is very reactive The reaction works well with aryl chloride One of merits in this protocol is

that carbonylation proceeds without using toxic CO gas and CO source is non-toxic alcohol More

detailed mechanistic studies using 13

C-enriched or deuterated alcohol will be discussed

References

1 Jun C -H Chem Soc Rev 2004 33 610-618

2 Park Y J Park J -W Jun C -H Acc Chem Res 2008 41 222-234

69

OC8

RADICAL-CATIONS OF ACETYLENE COMPOUNDS IN CARBON-

CARBON BOND FORMING REACTIONS

AV Vasilyev

Saint Petersburg State Forest Technical University Institutsky per 5 Saint Petersburg 194021

Russia Saint Petersburg State University Institute of Chemistry

Radical-cations of acetylene compounds A generated under oxidation of alkynes I in systems

PbO2-strong acid (CF3CO2H HF HSO3F) are key reaction intermediates in various new carbon-

carbon bond forming processes [1-6]

Depending on structure the species A lead to formation of a variety of products II-VII When

substituents X are moderate electron acceptors CO2R COAr COR PO(OEt)2 trans-ethenes II are

stereoselectively formed In case of stronger acceptors furan derivatives III (X = COCF3

СОCO2Et) or diketones IV (X = CF3) are formed

In different acidic systems radical-cations of diarylacetylenes (X = Ar) give unsaturated diketones

V (in CF3CO2H) butadiene difluiorides VI (in HF) or dichlorides VII (in HSO3F followed by

quenching in HClaquaconc) The last ones are electro-cyclically converted into naphthalenes VIII

C

C C

C

Ar Ar

FF

Ar Ar

C C

Ar

C C

Ar

Cl Cl

Ar Ar

CC

C

O O

C

Ar Ar

ArAr

Cl

Ar

Ar

Ar

R

H+ = CF3CO2H

H+ = HF

1 H+=HSO3F 2 HCl

VI

VIII

X = COCF3

COCO2EtC

OX

C C

C

OC

Ar

Ar Y

C

OX

C C

C

OX

Ar

ArX = CO2Alk

COAr COMe

PO(OEt)2

C C X

C CAr

I

A

III

II-e

Ar

X

PbO2H+

CF3F3C

C C

C

O O

C ArArHH

X = CF3

Y = CF3 CO2Et

X = Ar

IVV

X = Ar

X = Ar

VII

[1] Vasilyev AV Rudenko AP Russ J Org Chem (in Engl) 1997 V33 P 1555-1584

[2] Shchukin AO Vasilyev AV Fukin GK Rudenko AP Russ J Org Chem (in Engl)

2007 V43 P1446-1450

[3] Vasilyev AV Aristov SA Fukin GK Kozhanov KA Bubnov MP Cherkasov VK Russ

J Org Chem (in Engl) 2008 V44 P 791-802

[4] Vasilyev AV Shchukin AO Walspurger S Sommer J Eur J Org Chem 2008 4632

[5] Vasilyev AV Rudenko AP Russ J Org Chem (in Engl) 2010 V46 P1282-1289

[6] Alkhafaji HMH Vasilyev AV Ryabukhin DS Rudenko AP Muzalevskiy VM

Nenajdenko VG Russ J Org Chem (in Engl) 2013 V49 P 621-623

70

OC9

ACTIVATION OF Ru-BASED OLEFIN METATHESIS CATALYSTS

A Poater1 L Cavallo

2

1 - Institut de Quimica Computacional i Catаlisi and Departament de Quimica Universitat de

Girona Campus de Montilivi E-17071 Girona Catalonia Spain

2 - Kaust Catalysis Center Physical Sciences and Engineering Division King Abdullah University

of Science and Technology Thuwal 23955-6900 Saudi Arabia

In recent years olefin metathesis catalyzed by N-heterocyclic carbene ruthenium complexes has

attracted remarkable attention as a versatile tool to form new C=C bonds[1] The last developed

(pre)catalysts show excellent performances and this achievement has been possible because of

continuous experimental and computational efforts to understand the laws controlling the behavior

of these systems This perspective talk rapidly traces the ideas and discoveries that computational

chemistry contributed to the development of these catalysts with particular emphasis on catalysts

presenting a N-heterocyclic carbene ligand Specifically one of the most important challenges in

ruthenium-catalyzed olefin metathesis is to increase the stability of the catalysts under reaction

conditions and this hopefully without loss of activity Special interest has been addressed to study

the activation of the second-generation Grubbs catalysts which has clarifier either a dissociative or

an interchange mechanism is feasible[2]

Although in the solid state most ruthenium-based olefin metathesis catalysts are stable to oxygen

and moisture in solution decomposition usually occurs readily Understanding the decomposition

routes of catalysts is extremely important as any insight gained in this area can guide catalyst design

efforts to participate then in the synthesis of drugs[34] Furthermore new challenging projects

plan to modify the structure of the NHC ligands or replace this ligand by alkylidene ligands and

even the substitution of the metal is a goal moving to more environmentally friendly metals

[1] G C Vougioukalakis R H Grubbs Chem Rev 110 1746 (2010)

[2] C A Urbina-Blanco A Poater T Lebl S Manzini A M Z Slawin L Cavallo S P Nolan

J Am Chem Soc 135 7073 (2013)

[3] S Manzini C A Urbina-Blanco A Poater A M Z Slawin L Cavallo S P Nolan Angew

Chem Int Ed 51 1042 (2012)

[4] S Manzini A Poater D J Nelson L Cavallo S P Nolan Chem Sci 5 180 (2014)

71

OC10

CHEMICAL REACTIVITY IN PROTEINS AND WATER QMMM MD

INSIGHTS INTO EFFECTS OF LOCAL STRUCTURAL ENVIRONMENTS

ON BOND CLEAVAGE

Y Zhao BJ Wang RB Wu ZX Cao

Department of Chemistry Xiamen University Xiamen 361005 China

Water and proteins play a quite important role in chemical and biological processes In past few

years we carried out a systematic investigation on the effect of local structural environments on

reactivity towards hydrolysis C-N C-O and C-H bond cleavages in proteins and water Using

Born-Oppenheimer ab initio QMMM MD simulations a state-of-the-art approach to simulating

enzymes we have investigated the structural features of zinc enzymes nucleoside hydrolase and

deaminase and plausible enzymatic mechanisms The molecular complexity of active domain in

enzyme and roles of conserved residues and protein environments in enzymatic catalysis have been

explored In particular the different coordination modes and fast ligand exchanges of zinc

coordination has been suggested to be one key catalytic feature of the zinc ion and the chelation

mode of hydroxamate with the zinc ion in HDACs is modulated by water access to the linker

binding channel This new insight into the interplay between the linker binding and the zinc

chelation emphasizes its importance for the development of new class-IIa-specific HDAC

inhibitors Our calculations indicate that the reliable theoretical treatment on the water-mediated

proton transfer and most hydrolysis reactions of carbonyl compounds such as aldehydes ketones

esters amides the carboxylic acids and their derivatives requires use of the large basis set and

suitable cluster-continuum model The effects of solvent and structural modification on hydration

and hydrolysis of carbonyl compounds have been discussed

Acknowledgements This work was supported by the National Science Foundation of China

(21133007 and 21373164) and the Ministry of Science and Technology (2011CB808504)

References

1 N Chen H Ge J Xu Z Cao and R Wu Biochim Biophys Acta 2013 1834 1117

2 R Wu W Gong T Liu Y Zhang and Z Cao J Phys Chem B 2012 116 1984

3 B Wang and Z Cao Chem Eur J 2011 17 11929

4 B Wang and Z Cao Angew Chem Int Ed 2011 50 3266

5 R Wu Z Lu Z Cao and Y Zhang J Am Chem Soc 2011 133 6110

6 Y Zhao N Chen R Wu and Z Cao 2013 submitted

72

OC11

MECHANISM OF INTRAMOLECULAR HECK REACTION BY DENSITY

FUNCTIONAL THEORY

A Ayyappan D Yogeswara Rao

Indian Institute of Technology Kharagpur Department of Chemistry West Bengal 721392 India

Heck Reaction the palladium-catalyzed C-C coupling between aryl halides or vinyl halides and

activated alkenes in the presence of a base is widely used in syntheric chemistry Intramolecular

version of Heck reaction is a route to the generation carbocycles that are scaffolds of many

important natural products and biologically active molecules Although the mechanism of

intermoelcular Heck reactions is well established the intramelecular variant is not analyzed in detail

for its mechanistic features Using Density Functional Theory computations we have explored the

the catalytic cycle of intramolecular Heck reaction that involves oxidative addition migratory

insertion (cyclization) and β-hydride elimination (See Figure) Two pathways were analyzed which

differ in their initial coordination face (Re or Si) of the terminal alkene with the metal centre The

choice of pathway is not evident from free energy profile because one of the pathways have higher

barrier for oxidative addition the other requires high activation energy for β-hydride elimination

Detailed analysis of the mechanism will be presented In addition our attempts to analyze such

complex reaction mechanisms by kinetic simulations will be discussed

Figure Catalytic cycle for the intramolecular Heck reaction

73

OC12

CYCLODIMERIZATIONS OF DONOR-ACCEPTOR CYCLOPROPANES

SHORTCUT APPROACH TO COMPLEX RING SYSTEMS

EM Budynina OA Ivanova AO Chagarovskiy IV Trushkov

Moscow State University Department of Chemistry Moscow Russia

Cyclodimerization is among the most challenging and fascinating reactions providing significant

increase in structural complexity within one operation step in highly stereoselective manner and

occurring both in vivo and in vitro In organic synthesis among typical substrates that undergo

cyclodimerizations donor-acceptor (DA) cyclopropanes1 in which small ring is vicinally activated

with donor and acceptor groups occupy a special place Currently at least dozen types of Lewis

acid-triggered cyclodimerization of such DA cyclopropanes as 2-(het)aryl-cyclopropane-11-

diesters are known which open rapid approaches to diverse ring compounds including complex

polycyclic and bridged molecular systems2

Recently on basis of (3+3)-cyclodimerizations of 2-arylcyclopropane-11-diesters we developed

straightforward and efficient approaches to 14-diarylcyclohexanes 1-aryltetralins or 910-

dihydroanthracenes2a

(3+2)-Cyclodimerizations of similar cyclopropanes provide an easy access to

diarylcyclopentanes2bc

and arylindanes2d

Cyclodimerizations of 3- and 4-indolyl-derived DA

cyclopropanes allows for the construction of complex tetra- and heptacyclic cores of bisindoles2e

1 a) Reissig H-U Zimmer R Chem Rev 2003 103 1151 b) De Simone F Waser J

Synthesis 2009 3353 c) Melrsquonikov MYa Budynina EM Ivanova OA Trushkov IV

Mendeleev Commun 2011 21 293 d) Schneider TS Kaschel J Werz DB Ang Chem Int

Ed 2014 53 101002anie201309886

2 a) Ivanova OA Budynina EM Chagarovskiy AO Trushkov IV Melnikov MYa J

Org Chem 2011 76 8852 b) Chagarovskiy AO Ivanova OA Budynina EM Trushkov

IV Melnikov MYa Tetrahedron Lett 2011 52 4421 c) Novikov RA Korolev VA

Timofeev VP Tomilov YuV Tetrahedron Lett 2011 39 4996 d) Ivanova OA Budynina

EM Skvortsov DA Limoge M Bakin AV Chagarovskiy AO Trushkov IV

Melnikov MYa Chem Commun 2013 49 11482 e) Ivanova OA Budynina EM

Chagarovskiy AO Rakhmankulov ER Trushkov IV Semeykin AV Shimanovskii NL

Melnikov MYa Chem Eur J 2011 17 11738 f) Novikov RA Tarasova AV Korolev

VA Timofeev VP Tomilov YuV Ang Chem Int Ed 2014 53 3187 g) Novikov RA

Tomilov YuV Helv Chim Acta 2013 96 2068

74

OC13

USING RING STRAIN RELEASE FOR ALLEVIATION OF

TRANSANNULAR STRAIN SMALL RING-TEMPLATED SYNTHESIS OF

MEDIUM HETEROCYCLES

M Rubin M Rubina A Edwards P Ryabchuk

University of Kansas Department of Chemistry

A highly efficient diastereocenvergent reaction of bromocyclopropanes with various nucleophiles

have been recently developed in our laboratories1-7

This reaction involves a base-assisted

dehydrohalogenation to produce a highly reactive cyclopropene intermediate which undergoes

subsequent nucleophilic addition across the strained C=C bond Different intramolecular modes of

this reaction will be presented Possibilities for assembly of heterocyclic scaffolds with various ring

sizes including enantiomerically pure medium heterocycles will be demonstrated The mechanistic

aspect of this transformation and the means of controlling its diastereoselectivity will be discussed

Br

Nu

R

O

N O HN

O

R

R

Me

O

BaseTHF

18-crown-6 (cat)

t-BuOKTHFKOHTHF

t-BuOK DMSO

Ar Me

O

N

R

O

H

H

8-membered 7-10-membered

8-9-membered

N

Ph

Ph

O

t-BuOK THF

5-membered

O

O

R

R8-membered

O

O

O

Me

NH

HNO

Me

15-memberedt-BuOK DMSO

t-BuOK THF

References

[1] Alnasleh B K Sherrill W M Rubina M Banning J Rubin M J Am Chem Soc 2009

131 6906-6907

[2] Banning J E Prosser A R Rubin M Org Lett 2010 12 1488-1491

[3] Prosser A R Banning J E Rubina M Rubin M Org Lett 2010 12 3968-3971

[4] Banning J E Prosser A R Alnasleh B K Smarker J Rubina M Rubin M J Org

Chem 2011 76 3968-3986

[5] Ryabchuk P Rubina M Xu J Rubin M Org Lett 2012 14 1752-1755

[6] Banning J E Gentillon J Ryabchuk P Prosser A R Rogers A Edwards A Holtzen

A Babkov I A Rubina M Rubin M J Org Chem 2013 78 7601-7616

[7] Ryabchuk P Edwards A Gerasimchuk N Rubina M Rubin M Org Lett 2013 15

6010-6013

75

OC14

THE STRATEGY FOR ATOM ECONOMICAL REDUCTIVE ADDITION

DEOXYGENATION

D Chusov PN Kolesnikov VI Maleev NZ Yagafarov

ANNesmeyanov Institute of Organoelement Compounds of Russian Academy of Sciences

Herein we present the concept of using carbon monoxide for atom economical reductive addition

deoxygenation without external hydrogen source [1] We are utilizing this idea by showing that N-

H and C-H bonds of the reagents could be used as hydrogen source (Fig 1)

Figure 1

References

D Chusov B List Angew Chem Int Ed 2014 53 DOI 101002anie201400059

76

OC15

DINUCLEAR CATALYSIS ACCELERATED METAL-DEPENDENT RING-

OPENING POLYMERIZATION OF LACTIDE

E Kirillov

Universite de Rennes 1 UMR 6226 - CNRS 35042 Rennes France

Multinuclear olefin polymerization catalysts (incorporating several active metal centers in one and

the same molecule) have recently emerged as a distinct and brand new class of molecular catalysts 1

Implicit cooperative behavior2 of two or more metal centers in active species of these systems can

contribute to enhanced performance (with respect to mononuclear analogues) in terms of activity

chain-transfer kinetics and also monomers selectivity in copolymerization reactions

Dinuclear complexes of aluminum and indium with a bis(phenoxy-imine) platform have been

synthesized and used in the polymerization of lactide3a

Kinetic studies demonstrated that the

dialuminum precursor (Scheme 1) provides a more favorable reaction pathway in terms of

activation free energy than that of directly related monoaluminum systems3b

No similar trend was

observed with the corresponding diindium monoindium systems which was attributed to a

dissimilar ROP mechanism Details of the mechanisms and key factors of the dinuclear catalysis

will be discussed

Scheme 1 A dinuclear aluminum system enables a 5-to-10 fold boost in activity when compared to

its monoaluminum analogues

1 Delferro M Marks T J Chem Rev 2011 111 2450

2 Bratko I Goacutemez M Dalton Trans 2013 42 10664

3 (a) Normand M Roisnel T Carpentier J-F Kirillov E Chem Commun 2013 49 11692

(b) Normand M Dorcet V Kirillov E Carpentier J-F Organometallics 2013 32 1694

77

OC16

RECENT METHODOLOGICAL DEVELOPMENTS FOR THE QUANTUM

CHEMICAL STUDY OF COMPLEX SYSTEMS

S Irle

Nagoya University Department of Chemistry Nagoya Japan

The structural complexity of molecular clusters increases with size due to the associated rapidly

growing configuration space Two examples are realized in i) the transition from molecular to bulk

systems and ii) in the simulation of extended biosystems In such systems traditional quantum

chemical approaches of investigations are hampered by the vastly increasing computational cost

even considering ever-growing supercomputer capabilities Computationally inexpensive yet

accurate schemes such as the density-functional tight-binding (DFTB) method [1] and there linear

scaling versions promise here a significant advantage

We have recently engaged in developing novel methodologies for systems with increasing

structural complexity driven by motivation from experimental studies In this presentation we will

review a) the Kick-fragment-based ldquoKick3rdquo conformationally aware approach for studying

molecular [2] and ionic liquid clusters with increasing size and our implementation of the fragment

molecular orbital (FMO) method [3] with DFTB called ldquoFMO-DFTBrdquo in the popular GAMESS-

US quantum chemistry package [4] The computational effort of the method scales nearly linearly

with system size with a negligible pre-factor and allows the efficient massively-parallel quantum

chemical geometry optimization and direct molecular dynamics (MD) simulations of systems

containing several tens of thousands of atoms in particular when fragments consist of units with

less than 50 atoms [5] The method should be particularly useful to predict structures of new

artificial peptides and proteins predict enzymatic reaction pathways estimate free energy

contributions along pathways where large parts or even the entire protein including surrounding

water is treated quantum chemically and to simulate the effects of highly polarizable andor

charged solvents in explicit-solvent MD simulations

Unlike other linear scaling schemes such as divide and conquer approaches (DC) FMO-DFTBs

very design allows the insightful decomposition of interaction energies between ligands and

proteins in terms of electrostatics exchange-repulsion charge transfer dispersion and solvent

screening contributions in a straightforward manner

[1] M Gaus Q Cui M Elstner J Chem Theory Comput 7 931 (2011)

[2] M A Addicoat S Fukuoka A J Page S Irle J Comput Chem 34 2591 (2013)

[3] D G Fedorov T Nagata K Kitaura Phys Chem Chem Phys 14 7562 (2012)

[4] M W Schmidt K K Baldridge J A Boatz S T Elbert M S Gordon J H Jensen S

Koseki N Matsunaga K A Nguyen S Su T L Windus M Dupuis and J A Montgomery

Jr J Comput Chem 1993 14 1347 httpwwwmsgameslabgovgamessindexhtml

[5] Y Nishimoto D G Fedorov S Irle submitted

78

OC17

QUANTUM CHEMICAL MODELING IN STUDIES OF MOLECULAR

MECHANISMS OF ENZYME CATALYSIS

AV Nemukhin

Chemistry Department MV Lomonosov Moscow State University Moscow 199991 Russia NM

Emanuel Institute of Biochemical Physics Russian Academy of Sciences Moscow Russia

Recent results [1-3] of modeling chemical transformations in enzyme active sites using quantum-

based approaches will be discussed We apply quantum mechanicsmolecular mechanics (QMMM)

approaches to compute minimum energy pathways connecting enzyme-substrate and enzyme-

product complexes Appropriate crystal structures from the Protein Data Bank usually serve as a

source of coordinates of heavy atoms to create molecular model systems After in silico

construction of a three-dimensional full-atom model evolution of the model system along carefully

selected reaction coordinates is analyzed

Several examples of such modeling will be presented The complete cycle of chemical

transformations in penicillin acylase a unique enzyme that belongs to the recently discovered

superfamily of N-terminal nucleophile hydrolases with its most specific substrate penicillin G

leading to formation of 6-aminopenicillanic and phenylacetic acids [1] will be presented Keton-

ketal transformations at the active site of matrix metalloproteinases characterized computationally

[2] may be explored to propose specific inhibitors Chemical reactions in photoreceptor proteins

constitute an active field of application of QMMM modeling the case of BLUF domains will be

discussed [3]

Simulation results of guanosine triphposphate hydrolysis (GTP) by small GTPases icluding Ras

protein will be in focus According to newly obtained data the molecular events of the chemical

steps upon GTP hydrolysis include (i) cleavage of the phosphorus (Pγ) -oxygen bond in GTP upon

approach of the properly aligned catalytic water molecule producing GDP (ii) formation of a new

chemical bond between phosphorus and oxygen of water (iii) redistribution of protons between

reacting species leading to inorganic phosphate Pi

References

[1] Grigorenko BL Khrenova MG Nilov DK Nemukhin AV Švedas VK Catalytic Cycle of

Penicillin Acylase from Escherichia coli QMMM Modeling of Chemical Transformations in

the Enzyme Active Site upon Penicillin G Hydrolysis ACS Catal 2014 V 4 P 2521ndash2529

[2] Khrenova MG Nemukhin AV Savitsky AP Computational Characterization of Ketone-

Ketal Transformations at the Active Site of Matrix Metalloproteinases J Phys Chem B 2014

V 118 P 4345-4350

[3] Khrenova MG Nemukhin AV Domratcheva T Photoinduced Electron Transfer Facilitates

Tautomerization of the Conserved Signaling Glutamine Side Chain in BLUF Protein Light

Sensors J Phys Chem B 2013 V 117 P 2369-2377

79

OC18

EXCITED STATES AND MOLECULAR INTERACTIONS IN PROTEINS

AND SOLUTIONS

JH Hasegawa

Catalysis Research Center Hokkaido University Sapporo Japan

Solvatochromism and fluorescent solvatochromism are well-known phenomena and there are rich

accumulations in experimental publications Color tuning in proteins such as human color vision

and fluorescent proteins could be also classified to solvatochromism but with a specific

environment where anisotropic molecular interactions play important roles

We have studied biological color tuning with the SAC-CIMM calculations in which MM

description was adopted for the environmental effect This classical description for the environment

works very well for explaining the color tuning mechanisms

In some cases however environmental electronic structure effect becomes important To

investigate the origin of the QM effect we propose a scheme based on the wave function theory

with a MO localization scheme The role of the environmental electronic effect was analyzed in

terms of amino acidsrsquo orbital delocalizations excitonic interactions excited-state polarization and

dispersion interactions In the presentation we would show some results of pilot applications

80

OC19

CATIONIC GOLD-CATALYZED HETEROANNULATIONS

EV Van Der Eycken

University of Leuven (KU Leuven) Department of Chemistry Leuven Belgium

Gold catalysis is one of the fast growing research topics of modern organic chemistry In this

context gold-catalyzed carbocyclization and heteroannulation strategies have recently attracted

much attention due to the selective and efficient activation of the C-C triple bond towards a wide

range of nucleophiles Moreover the combination of multicomponent reactions with gold catalysis

gives access to complex molecular architectures in few steps as compared to traditional multistep

processes We will comment on our recent findings in this field A concise route to indoloazocines1

via a sequential Ugigold-catalyzed intramolecular hydroarylation2 will be presented A diversity-

oriented approach to spiroindoles via a post-Ugi gold-catalyzed diastereoselective domino

cyclization3 will be described (Scheme) as well as a regioselective approach for the synthesis of

pyrrolopyridinones and pyrroloazepinones employing a gold(I)platinum(II) switch4

N

O R3

H2N

R4

COOHR5

NC+

i) Ugi-4CR

NN

N

R5

O

O R3

(+-)

H

R1

R2

R2

R4

R1ii) cationic gold rt

13 examplesup to 80 yield

References

1 Synthesis of Azocino[54-b]indoles via Au-Catalyzed Intramolecular Alkyne Hydroarylation V

A Peshkov O P Pereshivko E V Van der Eycken Adv Synth Cat 354 2841-2848 2012

2 Concise route to indoloazocines via a sequential Ugigold-catalyzed intramolecular

hydroarylation S G Modha D D Vachhani J Jacobs L Van Meervelt E V Van der

Eycken Chem Commun 48 (52) 6550ndash6552 2012

3 Diversity-Oriented Approach to Spiroindolines Post-Ugi Gold-Catalyzed Diastereoselective

Domino Cyclization S G Modha A Kumar D D Vachhani J Jacobs S K Sharma V S

Parmar L Van Meervelt E V Van der Eycken Angew Chem Int Ed 51 9572-9575 2012

4 Gold(I) and Platinum(II) switch A post-Ugi intramolecular hydroarylation to pyrrolopyridinones

and pyrroloazepinones S G Modha A Kumar D D Vachhani S K Sharma V S Parmar E

V Van der Eycken Chem Comm 48 10916-10918 2012

81

OC20

Pd-SUPPORTED BIMETALLIC COMPOSITIONS FOR

STEREOSELECTIVE LIQUID PHASE SEMI-HYDROGENATION OF

DIPHENYLACETYLENE

IS Mashkovsky1 AV Sergeeva

1 OV Turova

1 MN Vargaftik

2 NYu Kozitsyna

2 AYu

Stakheev1

1 - Zelinsky Institute of Organic Chemistry RAS Moscow Russia

2 - Kurnakov Institute of General and Inorganic Chemistry RAS Moscow Russia

This study was focused on the development of the efficient catalyst for selective semi-

hydrogenation of internal alkene Diphenylacetylene (DPA) was used as a model compound The

catalytic compositions based on Pd-Zn Pd-Co Pd-Ni were investigated The samples were

prepared via two techniques (1) on the basis of palladium acetate heterobimetallic complexes as

precursors and (2) using traditional co-impregnation by individual metal salts It was found that the

systems based on bimetallic acetate complexes exhibited a substantial increase in selectivity to

alkene and cis-isomer formation at high conversion of the parent alkyne (DPA) albeit at the

expense of some decrease in the activity The detailed physicochemical study with TEM-EDS

SEM-EDS EXAFS and IR-spectroscopy reveals that the use of heterobimetallic acetate complex as

a precursor allows us to avoid metallic phase segregation during the reduction treatment of the

catalyst which ensures high homogeneity of bimetallic particles and leads to enhanced selectivity

Financial support was provided by RFBR foundation grants 12-03-31487 13-03-12176

Рис 1 Dependency of selectivity to cis-isomer and alkene on DPA conversion for PdAl2O3

catalyst modified with Co Zn and Ni in liquid phase DPA hydrogenation

Se

lecti

vit

y t

o c

is-i

so

me

r

0

10

20

30

40

50

60

70

80

90

100

70 80 90 100

0

10

20

30

40

50

60

70

80

90

100

70 80 90 100

DPA conversion

093PdAl2O3

093Pd-052ZnAl2O3

093Pd-053NiAl2O3

093Pd-053CoAl2O3

DPA conversion

Se

lecti

vit

y t

o a

lke

ne

H

H

H

H

H

H

+

H

H

H

H

+

093PdAl2O3

093Pd-052ZnAl2O3

093Pd-053NiAl2O3

093Pd-053CoAl2O3

82

OC21

DESIGN OF NANOSTRUCTURES ON THE BASIS OF TWO

PHARMACOPHORIC FRAGMENTS - FULLERENE AND PIPERIDINE

DERIVATIVES

GV Grishina IS Veselov IV Trushkov

M V Lomonosov Moscow State University Department of Chemistry

This communication is described the creation of a new nanobiosystems with high antivirus potential

based on the two pharmacophoric fragments - derivatives of fullerene C60 and piperidine ligands

Design of nanoadditive on the basis of two pharmacophoric fragments - functional derivatives of

trans-34-dihydroxypiperidine and organically modified by fullerene C60 can be a very promising

bioactive substances Such a perspective is related to using first as ligands several trans-34-

dihydroxylated piperidines already demonstrated anti-HIV activity and secondly the uniqueness of

fullerene spheroid significantly reduce the toxicity of biologically active adducts We believed that

binding of two biologically active units in the same system will be very useful and promising

N

YX

COOEtON

Me NY

X

1 X = H Y = OH

2 X = Y = OH

3 X =NHR Y = OH

4

Monoadducts 1-4 have obtained by the Benguel and Prato reactions respectively and have since

received 12 new fullerene adducts based on the derivatives of the trans-34-dihydroxypyridine and

trans-4-amino-3-hydroxypiperidines Isolation and identification of these adducts were made using

column and preparative chromatography on silica gel structure and stereochemistry were

established with the involvement required in each case spectral methods including mass

spectrometry and МАLDI X-ray analysis and 1H

13C NMR The main difficulty in undertake

researches consisted of significant differences reactivity due to high lipophilicity derivatives of

fullerene and high hydrophilicity piperidine ligands To reduce this difference we have modified

both fragments introduction to piperidine ligands andor in the molecule organically modified

fullerenes functions andor linkers which facilitated further obtaining of target adducts For some

samples of adducts managed to get soluble in alcohol salts A very important factor has been the

elucidation of the impact of structural and stereochemical factors on possible synergies in the

adduct investigation Target adducts are a new type of nanostructures for medical chemistry with

great pharmacological potential

83

OC22

CHIRASAC STUDY ON CHIRAL SPECTROSCOPY AND PHOTOBIOLOGY

H Nakatsuji T Miyahara

Quantum Chemistry Research Institute (QCRI) 1-36 Goryo-Oohara Nishikyo-ku Kyoto 615-8245

Japan

Weak interactions of molecules with solvents andor environments are of crucial importance in

material science and biology but rather difficult to investigate quantitatively Circular dichroism

(CD) spectra reflect sensitively the conformational structures of chiral molecules their (weak)

interactions with solvents andor proteins etc The SAC-CI method gives their CD spectra very

reliably From this fact the SAC-CI method is a useful tool to investigate the conformational

geometries of chiral molecules their interactions with environments etc by comparing their

experimental and SAC-CI theoretical CD spectra We initiated a systematic molecular technology

called ChiraSac (Chirality + SAC-CI) project (see Figure 1) by using the SAC-CI code and other

highly reliable and useful codes on ldquoGAUSSIANrdquo suit of programs [1] We have already applied

this project successfully to several topics of chiral spectroscopy and photobiology [2-4] We will

present here conformational dependence of α-Hydroxyphenylacetic Acid and similarities and

differences between RNA and DNA etc as some recent applications of ChiraSac to chiral

spectroscopy and photobiology

References

[1] M J Frisch G W Trucks H B Schlegel G

E Scuseria M A Robb J R Cheeseman G

Scalmani V Barone B Mennucci G A

Petersson et al Gaussian 09 Gaussian Inc

Wallingford CT 2009

[2] Circular Dichroism Spectra of Uridine

Derivatives ChiraSac Study Tomoo

Miyahara Hiroshi Nakatsuji and Takehiko

Wada J Phys Chem A 118 2931-2941

(2014)

[3] Conformational Dependence of the Circular

Dichroism Spectrum of α-Hydroxyphenyl-

acetic Acid A ChiraSac Study Tomoo

Miyahara and Hiroshi Nakatsuji J Phys

Chem A 117 14065- 14074 (2013)

[4] Helical Structure and Circular Dichroism

Spectra of DNA A Theoretical Study T

Miyahara H Nakatsuji and H Sugiyama J

Phys Chem A 117 42-55 (2013)

84

OC23

A DFT ANALYSIS ON THE ELECTRONIC PROPERTIES OF

METHYLAMMONIUM LEAD IODIDE PEROVSKITE

K Yamashita1 G Giorgi

1 J Fujisawa

2 H Segawa

2

1 - Department of Chemical System Engineering The University of Tokyo Japan

2 - Research Center for Advanced Science and Technology The University of TokyoJapan

Methylammonium (MA) lead iodide perovskite (CH3NH3PbI3) plays an important role in light

absorption and carrier transport in efficient organicminusinorganic perovskite solar cells [1] In my talk

the first theoretical estimation of effective masses of photocarriers and the role of MA cation in

CH3NH3PbI3 will be discussed

Spin-polarized DFT calculations have been performed with the generalized gradient approximation

From the charge density of the two-fold degenerate states ((a) and (b)) of CBM and those ((c) and

(d)) of VBM one can see that photogenerated electrons around CBM and holes around VBM exist

separately results related to the ambipolar transport nature of the material Effective masses of

photogenerated electrons and holes are estimated to be me =023m0 and mh = 029m0

respectively including spinminusorbit coupling (SOC) effects This result is consistent with the long-

range ambipolar transport property and with the larger diffusion constant for electrons compared

with that for holes in the perovskite which enable efficient photovoltaic conversion [2]

We also have focused our attention on the MA cation and studied the role it plays in the

electronicoptical features of the perovskite paying attention mainly to the iodide compound [3] A

comparison is performed between the electronic properties of MAPbI3 organic-inorganic perovskite

and those of the purely inorganic CsPbI3

References 1 J Bisquert J Phys Chem Lett 4 2597 (2013)

2 G Giorgi J Fujisawa H Segawa K Yamashita J Phys Chem Lett 4 4213 (2013)

3 G Giorgi J Fujisawa H Segawa K Yamashita J Phys Chem 118 12176 (2014)

85

OC24

A HYBRID MCMD REACTION METHOD WITH RARE EVENT-DRIVING

MECHANISM ATOMISTIC REALIZATION OF 2-CHLOROBUTANE

RACEMIZATION PROCESS IN DMS SOLUTION

M Nagaoka

Graduate School of Information Science Nagoya University Furo-cho Chikusa-ku Nagoya 464-

8601 Japan Core Research for Evolutional Science and Technology (CREST) Japan Science and

Technology Agency (JST) Honmachi Kawaguchi 332-0012 Japan ESICB Kyoto University

Kyodai Katsura Nishikyo-ku Kyoto 615-8520 Japan

We demonstrate a new efficient hybrid MCMD reaction method with a rare event-driving

mechanism as a practical lsquoatomisticrsquo molecular simulation of large-scale chemically reactive

systems (Figure 1) Application of the method to (R)-2-chlorobutane molecules in NN-

dimethylformamide (DMF) molecules starting in the optical pure state (100 ee) was found to

successfully provide such an atomistic state with ~0 ee the expected purity of (R)- to (S)-

enantiomers of the racemic mixture in chemical equilibrium [1]

This hybrid MCMD reaction method is promising for studies of various properties in chemically

reactive systems [2] and their stereochemistry as well

Figure 1 Schematic representation of the hybrid MCMD reaction method The curly curves

represent the molecular dynamical (MD) moves in phase space following the equations of motion

while the straight lines with arrows represent the Monte Carlo (MC) moves (or transitions) of the

system (right figure) whose dynamical moves would be extremely rare events In the left figure the

configurational distribution in equilibrium peq

is proportional to the exponential factor exp[-βU]

where U is the global potential function The right figure shows regional distributions eg preq

exp[-βUr] in region r etc The connecting points of the two kinds of moves (open circles) are

selected according to the criteria for chemical reaction occurrence Note that they do not represent

real connections since these points correspond to almost identical states in configuration space but

not in momentum space and with different configurational gradients Wrrarrs and Wsrarrt are the

transition probabilities from state r to s and from s to t respectively [1]

[1] Masataka Nagaoka Yuichi Suzuki Takuya Okamoto Norio Takenaka Chem Phys Lett 583

80 (2013)

[2] N Takenaka Y Suzuki H Sakai M Nagaoka J Phys Chem C 118 10874 (2014)

International Advisory Committee

H Alper University of Ottawa Canada

D Astruc University of Bordeaux France

J Dupont Institute of Chemistry Brazil

P J Dyson EPFL Switzerland

R G Finke Colorado State University USA

G C Fu California Institute of Technology USA

A Furstner Max Planck Institut fur Kohlenforschung Germany

V K Jain Bhabha Research Centre India

CW Jones Georgia Institute of Technology USA

P-H Leung Nanyang Technological University Singapore

C Najera Universidad de Alicante Spain

E-i Negishi Purdue University USA

L A Oro University of Zaragoza-CSIC Spain

R Poli Institut National Polytechnique France

V Snieckus Queens University Canada

M Taillefer Institut Charles Gerhardt France

A M Trzeciak University of Wroclaw Poland

Y Yamamoto Tohoku University Japan

Local Organizing Committee

ND Zelinsky Institute of Organic Chemistry RAS

M P Egorov Chairman

V P Ananikov Vice-chairman

A D Dilman

A M Sakharov

A Y Stakheev

AM Starosotnikov

A O Terentev

O V Turova

S G Zlotin

National Advisory Committee

G A Abakumov N Novgorod

I P Beletskaya Moscow

Y N Bubnov Moscow

V N Charushin Ekaterinburg

O N Chupakhin Ekaterinburg

A I Konovalov Kazan

V V Lunin Moscow

V I Minkin Rostov

O M Nefedov Moscow

V N Parmon Novosibirsk

O G Syniashin Kazan

V A Tartakovsky Moscow

B A Trofimov Irkutsk

M S Yunusov Ufa

N S Zefirov Moscow

Index

Plenary Lectures 7

Invited Lectures 22

Oral Communications 60

Posters 110

Authors Index 326

7

Plenary Lectures

8

9

PL1

THE APPLICATION OF PHOTOREDOX CATALYSIS TO NEW

TRANSFORMATIONS IN CHEMICAL SYNTHESIS

DWC MacMillan

Merck Center for Catalysis Princeton UniversityPrinceton NJ 08544

This lecture will discuss the advent and development of new concepts in chemical synthesis

specifically the combination of photoredox catalysis with organic catalysis This new approach to

ldquosynergistic catalysisrdquo will demonstrate that multiple yet separate catalytic cycles can be aligned to

generate activated intermediates that rapidly combine with each other thereby allowing new

approaches to enantioselective CndashC and C-heteroatom bond formation

We will also introduce an approach to the discovery of new chemical reactions that we term

accelerated serendipity Accidental or lsquoserendipitousrsquo discoveries have led to some of the most

important breakthroughs in scientific history many of which have directly affected human life

Given our overarching goal of developing fundamentally new and useful chemical transformations

using catalysis and by acknowledging the tremendous impact of serendipity in scientific discovery

we questioned whether this phenomenon could be forced or simulated and therefore employed as a

tool for reaction discovery

In this presentation we will describe several new transformations that have been discovered via

ldquoaccelerated serendipityrdquo that we expect will find widespread adoption throughout the field of

chemical synthesis Moreover we will further describe how mechanistic understanding of these

processes has led to the design of a valuable new yet fundamental chemical transformation

Acknowledgements Financial support was provided by NIHGMS (R01 01 GM093213-01) and kind gifts from Merck

Amgen and Abbott

10

PL2

GOLD CATALYSIS 20

ASK Hashmi

Organisch-Chemisches Institut Fakultaumlt fuumlr Chemie und Geowissenschaften Universitaumlt

Heidelberg Im Neuenheimer Feld 270 69120 Heidelberg Germany

Homogeneous catalysis by gold has developed to an important sector of catalysis research1

Initially efforts in methodology development clearly dominated in the last years also an increasing

number of applications in synthesis has been reported23

Efforts to understand the basic mechanism

of these reactions continuously accompanied the field4

For twelve years most of the reactions followed simple reaction mechanisms basing on the

interaction of one gold centre in a gold complex or organogold compound with the substrate

molecule In most of these reactions vinylgold or alkylgold intermediates are involved sometimes

also gold carbenoids

Now an entirely new family of reactions basing on the activation of the organic substrates by two

gold complexes at the same time (one -coordinated the other -coordinated) has been discovered

These open up entirely new synthetic possibilities and follow quite complex mechanisms These

mechanisms which are new to the field of organometallic chemistry will be discussed in detail

Some of the new reactions even allow positional selective CH activations of alkyl side chains as

exemplified below

The presentation will also contain results from computational chemistry

References

1 A S K Hashmi Chem Rev 2007 107 3180-3211

2 A S K Hashmi M Rudolph Chem Soc Rev 2008 37 1766-1775

3 M Rudolph A S K Hashmi Chem Soc Rev 2012 41 2448-2462

4 A S K Hashmi Angew Chem Int Ed 2010 49 5232-5241

11

PL3

HOW MUCH CATALYST DO WE NEED

C Bolm

Institute of Organic Chemistry RWTH Aachen University 52056 Aachen Germany

Various C-N- C-O- and C-C-bond forming reactions leading to cross coupling-type products can

be performed without transition metals In this presentation we will discuss cyclizations affording

benzimidazol-2-ones1 and indazoles

2 (eqs 1 and 2 respectively) Photochemical initiations (eq 3)

led us to other directions34

R1 X

NHN

O

R3

R2

N

N

R2

R3

R1

O

40 degC 24 h

X = I Br (Cl F)

(eq 1)

toluene RT 25 h

N

R2

HNR3X

N

N

R2

R3

R1 R1

TMS

O

R2

O

R1hn

CH2Cl2 RT O

O

R1R2

TMS

X = I Br

(eq 2)

(eq 3)

KOHDMSO

diamineK2CO3

Finally we will present mechanochemical activations in ball mills that allow reducing the catalyst

loadings in asymmetric organocatalyses5-7

References

1 a) Yuan Y Thomeacute I Kim S H Chen D Beyer A Bonnamour J Zuidema E Chang

S Bolm C Adv Synth Catal 2010 352 2892 b) Beyer A Reucher C M M Bolm C

Org Lett 2011 13 2876 c) Thomeacute I Bolm C Org Lett 2012 14 1892 d) Beyer A

Buendia J Bolm C Org Lett 2012 14 3948 e) Baars H Beyer A Kohlhepp S V Bolm

C Org Lett 2014 16 536

2 Thomeacute I Besson C Kleine T Bolm C Angew Chem Int Ed 2013 52 7509

3 a) Zhang H-J Becker P Huang H Pirwerdjan R Pan F-F Bolm C Adv Synth Catal

2012 354 2157 b) Becker P Priebbenow D L Zhang H-J Pirwerdjan R Bolm C J

Org Chem 2014 79 814 c) Becker P Priebbenow D L Pirwerdjan R Bolm C Angew

Chem Int Ed 2014 53 269

4 For a photochemical activation in a metal catalysis see Bizet V Buglioni L Bolm C

Angew Chem Int Ed DOI 101002anie201310790

5 a) Joumlrres M Mersmann S Raabe G Bolm C Green Chem 2013 15 612 See also in b)

Kleine T Buendia J Bolm C Green Chem 2013 15 160

6 For a video see httpwwwbeilsteintvtvpostasymmetric-organocatalysis-in-a-ball-mill

7 For a general overview see James S L Collier P Parkin I Hyett G Braga D Maini L

Jones B Friscic T Bolm C Krebs A Mack J Waddell D C Shearouse W C Orpen

G AdamsC Steed J W Harris K D M Chem Soc Rev 2012 41 413

12

PL4

ldquoMOLECULAR METATHESIS CATALYSTSrdquo AT THE DAWN OF

INDUSTRIAL IMPLEMENTATION

DE Fogg

University of Ottawa

Ruthenium-catalyzed olefin metathesis has enormous potential for impact on the chemical

enterprise in sectors ranging from pharma to specialty polymers and ldquogreenrdquo feedstocks

Phosphine-free metathesis catalysts particularly those of the Hoveyda type (HII see Figure 1)

occupy a position of increasing prominence In one of the most high-profile current applications of

metathesis chemistry transformation of seed oils into functionalized olefins HII significantly out-

performs the benchmark Grubbs catalyst GII [12]

despite the fact that the two catalysts generate a

common active species (A) Reports from pharma RampD indicate that HII also offers superior

performance in some demanding RCM applications (RCM = ring-closing metathesis)[3]

As these

and closely related molecular metathesis catalysts enter deployment in process chemistry

understanding the mechanistic basis of their performance takes on added importance

We will discuss potential contributors to the improved productivity of HII the absence of free

PCy3 the presence of the styrenyl ether ligand and operation of HII via interchange-associative

pathways The relevance of each of these factors will be considered in the context of demanding

ring-closing and cross-metathesis reactions

Figure 1 Molecular structure of an organometallic product

References

[1] Miao X Fischmeister C Dixneuf P H Bruneau C Dubois J L Couturier J L Green

Chem 2012 14 2179-2183

[2] Biermann U Bornscheuer U Meier M A R Metzger J O Schafer H J Angew Chem

Int Ed 2011 50 3854ndash3871

[3] van Lierop B J Lummiss J A M Fogg D E Ring-Closing Metathesis A How-To Guide

In Olefin Metathesis Theory and Practice Grela K Ed Wiley Weinheim 2014

13

PL5

REDUCTIONS WITH ORGANIC REAGENTS mdash THE ELECTRON AS A

CATALYST

A Studer

WWU Muenster Chemistry Germany

In the lecture reduction processes for generation of various radicals using different organic reagents

will be presented Reactions are generally conducted using stoichiometric SET-reagents However

also some catalytic variants will be presented In the presentation radical perfluoroalkylations and

azidations will be addressed Moreover the concept of using the electron as a catalyst will be

discussed and some examples provided

14

PL6

NANOELECTRONICS MOLECULAR METAL WIRES AND RELATED

MOLECULAR MATERIALS

SM Peng

Department of Chemistry National Taiwan University Taipei Taiwan

We have designed a series of new ligands such as oligo-α-pyridylamines and used them to

construct an unique class of quadruple helix of metal strings This achievement leads to a new

direction to the application of molecular wires in the nanoelectronics

The outline is as follows

I Linear Metal String Complexes (1)

Synthesis Structure Bonding

II Potential Application as Molecular Metal Wires amp Molecular Switches (2)

STM-bj Study on the Conductivity of Metal Strings

Comparative Study on the I-V Characterisics (Theory VS Experiment)

III Tuning of the Metal Strings (3-9)

Naphthyridyl Amino Ligands Low Oxidation Mixed Metal Strings

Asymmetrical Ligands Toward Molecular Rectifier

Heteronuclear Metal String Complexes

Chiral Quadruple Helixes

IV Conclusion

Fig1 Metal Strings of Oligo- -pyridylamido Ligands

1 C-Y Yeh C-C Wang Y-H Chen and S-M Peng in Redox Systems Under Nano-Space

Control Ed T Hirao Springer Germany 2006 Ch 5

2 I-W P Chen M-D Fu W-H Tseng J-Y Yu S-H Wu C-J Ku C-H Chen and S-M

Peng Angew Chem Int Ed Engl 2006 5414

3 (a) C-H Chien J-C Chang C-Y Yeh G-H Lee J-M Fang and S-M Peng Dalton Trans

2006 2106 (b) C-H Chien G-H Lee Y Song and S-M Peng Dalton Trans 2006 3249

4 M-M Rohmer I P-C Liu J-C Lin M-J Chiu C-H Lee G-H Lee M Benard X Lopez

S-M Peng Angew Chem Int Ed Engl 2007 46 3533

5 I P-C Li W-Z Wang and S-M Peng Chem Commun 2009 4323-4331

6 R H Ismayilov W-ZWang G H Lee C Y Yeh S A Hua Y Song M M Rohmer M

Beacutenard S-M Peng Angew Chem Int Ed 2011 50 2045-2048

7 I P-C Liu C-H Chen S-M Peng Bull Jpn Soc Coord Chem 2012 59 1-8

N N N N N

M M M M MX X

4

m

M = N i C o C r

m = 0 1 2 3

X = C l N C S

15

8 M-C Cheng C-L Mai C-Y Yeh G-H Lee S-M Peng Chem Commun 2013 49 7938-

7940

9 M-J Huang S-A Hua M-D Fu G-C Huang C Yin C-H Ko C-K Kuo C-H Hsu G-H

Lee K-Y Ho C-H Wang Y-W Yang I-C Chen S-M Peng C-h Chen Chem Eur J

2014 DOI 101002chem201400067

16

PL7

NEW CYCLOADDITION STRATEGIES BASED ON STRAINED AND

UNUSUAL MOLECULES

RL Danheiser

Department of Chemistry Massachusetts Institute of Technology Cambridge MA 02139 USA

Highly substituted carbocyclic and heterocyclic rings are key structural features in many

biologically significant and commercially important compounds Although classical synthetic

approaches to such compounds have generally relied on linear substitution strategies convergent

cycloaddition and annulation strategies have emerged as powerful alternative methods for the

assembly of highly substituted cyclic compounds The intrinsic convergent nature of cycloaddition

and annulation strategies facilitates the efficient assembly of highly substituted systems that would

have required long multistep routes using alternative methods

This talk will focus on the application of strained and unusual molecules as building blocks in

cycloaddition strategies for the construction of complex carbocyclic and heterocyclic compounds

The synthetic utility of highly unsaturated conjugated molecules such as vinylketenes conjugated

enynes vinylallenes allenylimines and iminoacetonitriles will be described as well as their

application in the total synthesis of natural products

17

PL8

SILICON TETHER MOTIF IN C-H ACTIVATION REACTIONS

V Gevorgyan

University of Illinois at Chicago

We have developed a set of new transition metal-catalyzed C-H activation methodologies

employing a silicon-tether motif These methods feature (a) use of silyl group as a tether between a

substrate and a reagent thus transforming intermolecular reaction into intramolecular reaction1-2

(b) employment of a silicon-tethered directing group which is traceless or easily convertable into

valuable functionalities3-8

(c) use of silyl-tethered hydrosilane reagent9-10

and (d) introduction of

new NSi-chelation concept that allows for a remote activation of aliphatic C-H bonds11

The scope of these transformations will be demonstrated and the mechanisms will be discussed

References

1 Huang C Gevorgyan V J Am Chem Soc 2009 131 10844

2 Huang C Gevorgyan V Org Lett 2010 12 2442

3 Chernyak N Dudnik A S Huang C Gevorgyan V J Am Chem Soc 2010 132 8270

4 Dudnik A S Chernyak N Huang C Gevorgyan V Angew Chem Int Ed 2010 49 8729

5 Huang C Chattopadhyay B Gevorgyan V J Am Chem Soc 2011 133 12406

6 Huang C Ghavtadze N Chattopadhyay B Gevorgyan V J Am Chem Soc 2011 133 17630

7 Gulevich A V Melkonyan F S Sarkar D Gevorgyan V J Am Chem Soc 2012 134

5528

8 Sarkar D Melkonyan F S Gulevich A V Gevorgyan V Angew Chem Int Ed 2013 52

10800

9 Kuznetsov A Gevorgyan V Org Lett 2012 14 914

10 Kuznetsov A Onishi Y Inamoto Y Gevorgyan V Org Lett 2013 15 2498

11 Ghavtadze N Melkonyan F S Gulevich A Huang C Gevorgyan V Nat Chem 2014 6

122

18

PL9

WERNER COMPLEXES A NEW CLASS OF CHIRAL HYDROGEN BOND

DONOR CATALYSTS FOR ENANTIOSELECTIVE ORGANIC REACTIONS

JA Gladysz

Department of Chemistry Texas AampM University PO Box 30012 College Station Texas 77842-

3012 USA

Salts of the chiral tris(ethylenediamine)-substituted octahedral trication [Co(en)3]3+

and related

species have played important historical roles in the development of inorganic chemistry and

stereochemistry12

As Werner described in 1912 the two enantiomers commonly designated and

can be separated by crystallization of the diastereomeric tartrate salts2 However despite the low

cost and ready availability of the building blocks there have been no applications in

enantioselective organic synthesis

NH2

NH2

H2N

H2N

NH2

H2N

Co3+

H2N

H2N

NH2

NH2

NH2

H2N

Co3+L D

We have found that [Co(en)3]

3+ and related cations can be rendered soluble in organic solvents by

using lipophilic anions such as BArfndash

3 Suitably functionalized derivatives act as highly

enantioselective catalysts for a variety of carbon-carbon bond forming reactions The mechanisms

involve outer sphere activation of the electrophile by hydrogen bonding to the NH moieties Other

types of metal-containing chiral hydrogen bond donors are also effective including a chelate of the

CpRuL fragment

H2N

H2N

NH2

NH2

NH2

H2N

Co3+ Ph

Ph

Ph

Ph

Ph

Ph

2Clndash BAr fndash

catNO2

NO2

OMe

O

MeO

O

Et3N acetone

10 molO O

OMeMeO

12 eq 0 degCX

X

Time (h)

Conversion ()

ee ()

15 gt99 88NO2

OMe

O

MeO

O

22 98 94NO2

OMe

O

MeO

O

O

Ph

H2N

H2N

NH2

NH2

NH2

H2N

Co3+ Ph

Ph

Ph

Ph

Ph

Ph

2BF4ndash BAr f

ndash

H2N

H2N

NH2

NH2

NH2

H2N

Co3+ Ph

Ph

Ph

Ph

Ph

Ph

2PF6ndash BAr f

ndash

Time (h)

Conversion ()

ee ()

10 94 90

7 98 97

Time (h)

Conversion ()

ee ()

4 gt99 86

4 gt99 94

L L L

1 Kauffman G B Coord Chem Rev 1974 12 105-149

2 Werner A Chem Ber 1911 44 1887-1898 and 1912 45 121-130

3 Ganzmann C Gladysz J A Chem Eur J 2008 14 5397-5400

4 Ghosh S K Ojeda A S Guerrero-Leal J Bhuvanesh N Gladysz J A Inorg Chem 2013

52 9369-9378

5 Thomas C Gladysz J A ACS Catalysis 2014 5 1134-1138

19

PL10

COMPLEXITY IN SIMPLICITY THE PROTOTYPE REACTIONS OF

CARBENE ANALOGS

MP Egorov

Zelinsky Institute of Organic Chemistry Russian Academy of Sciences Leninsky Prospect 47

Moscow 119991 Russia

20

PL11

SELECTIVELY ALKYLATED AND ARYLATED N-HETEROAROMATICS

VIA ACCEPTORLESS DEHYDROGENATIVE CONDENSATION

(ADC) REACTIONS

R Kempe

Lehrstuhl Anorganische Chemie II (Catalyst Design)University of Bayreuth Bavaria Germany

Dwindling reserves of crude oil and the resulting price increase of this and other fossil carbon

sources combined with environmental concerns have resulted in a call for the use of alternative

preferably renewable resources Aside from fuel ultimately a wide variety of chemical feedstocks

are derived from fossil sources Renewable lignocellulosic materials are indigestible and therefore

not useful as food products and can be processed to give alcohols and polyols These rather highly

oxidized hydrocarbons differ drastically in their chemical nature from the cracking products of

crude oil Thus there is a high demand for new reactions that utilize alcohols and convert them into

key chemicals Recently our group developed a sustainable catalytic pyrrole synthesis[1]

Secondary alcohols and amino alcohols are deoxygenated and linked selectively via the formation

of CndashN and CndashC bonds Two equivalents of hydrogen gas and two equivalents of water are

eliminated in the course of the reaction (Acceptorless Dehydrogenative Condensation ADC)

Alcohols based entirely on renewable resources can be used as starting materials The catalytic

synthesis protocol tolerates a large variety of functional groups which includes olefins chlorides

bromides organometallic moieties amines and hydroxyl groups Furthermore we have developed a

catalyst that operates efficiently under mild conditions This methodology could also be used to

synthesize selectively functionalized pyridines from alcohols[2] In the talk the development of

alcohol re-functionalization reactions and the design of catalyst systems that mediate these reactions

are discussed

[1] S Michlik R Kempe Nature Chem 2013 5 140

[2] S Michlik R Kempe Angew Chem Int Ed 2013 52 6450

21

PL12

THE CATALYST TODAY BIG BANG AND LIFE AFTER

IP Beletskaya

Lomonosov Moscow State University Department of Chemistry Moscow Russia

Nanocatalysis and catalysis by Lewis and Broensted acids will be considered in the lecture

22

Invited Lectures

23

24

IL1

CYCLIZATIONS OF ALKYNES FROM STEREOELECTRONICS TO

CASCADE TRANSFORMATIONS

IV Alabugin

Department of Chemistry and Biochemistry Florida State University Tallahassee Fl

One of the simplest organic functional groups the alkyne moiety is also one a useful starting point

for the design of cascade transformations which proceed through the formation of multiple C-C C-

H C-N and C-O bonds [1] In this talk I will illustrate how the revised stereoelectronic rules for

alkyne cyclizations [2] can be used for the bottom-up preparation of carbon nanostructures for

molecular electronics (ie graphene nanoribbons) In our approach alkyne chains of varying sizes

shapes and functionalities are built in a modular fashion and ldquozippedrdquo up into graphene

substructures via controlled cascades of all-exo or all-endo cyclizations [3]

Even in the presence of multiple functionalities alkyne cascades can be made chemoselective via

kinetic self-sorting of the pool of equilibrating radicals [4] Further synthetic opportunities are

presented by fusion of cyclization cascades with self-terminating fragmentations that allow use of

alkenes as synthetic equivalents of alkynes [5]

[1] Alabugin I V Gold B J Org Chem 2013 78 7777

[2] Alabugin I V Gilmore K Manoharan M J Am Chem Soc 2011 133 12608 Alabugin I

V Gilmore K Chem Commun 2013 49 11246

[3] Byers P M Rashid J I Mohamed R K Alabugin I V Org Lett 2012 14 6032 Byers

P J Am Chem Soc 2012 134 9609

[4] Mondal S Mohamed R K Manoharan M Phan H Alabugin I V Org Lett 2013 15

5650

[5] Mondal S Gold B Mohamed R K Alabugin I V Chemistry ndash Eur Journal 2014 in

print

25

IL2

ARTIFICIAL PHOTOSYNTHESIS USING TRANSITION METAL

COMPLEXES

O Ishitani

Department of Chemistry Tokyo Institute of Technology Japan

Both the problems of the global warming and shortage of the fossil fuels have brought about great

interest in photochemical utilization of CO2 with solar energy Efficient photocatalysts for CO2

reduction must be necessary for development of such an important technology

We have developed novel types of photocatalytic systems using metal complexes andor

semiconductors as a photocatalyst1 In this presentation I will focus on the architecture of two

types of the photocatalysts using transition metal complexes

(1) A mixed photocatalytic system including a ring-shaped Re(I) multinuclear complex as a

photosensitizer2

(2) Ru(II)-Re(I) and Ru(II)-Re(I) supramolecular photocatalysts3

The efficiency of the former photocatalytic system has been highest in the reported CO2-reduction

photocatalysts ( = 82) and the latter photocatalysts have been most robust (TON gt 3000)

References

1 (a) Yui T Tamaki Y Sekizawa K Ishitani O Photocatalytic reduction of CO2 from

molecules to semiconductors Top Curr Chem 2011 303 151-84 (b) Sekizawa K Maeda K

Domen K Koike K Ishitani O J Am Chem Soc 2013 135 4596

2 Morimoto T Nishiura C Tanaka M Rohacova J Nakagawa Y Funada Y Koike K

Yamamoto Y Shishido S Kojima T Saeki T Ozeki T Ishitani O J Am Chem Soc

2013 135 13266

3 (a) Gholamkhass B Mametsuka H Koike K Tanabe T Furue M Ishitani O Inorg

Chem 2005 44 2326 (b) Sato S Koike K Inoue H Ishitani O Photochem Photobiol Sci

2007 6 454 (c) Koike K Naito S Sato S Tamaki Y Ishitani O J Photochem Photobiol

A Chem 2009 207 109 (d) Tamaki Y Watanabe K Koike K Inoue H Morimoto T

Ishitani O Faraday Discuss 2012 155 115 (e) Tamaki Y Morimoto T Koike K Ishitani

O Proc Natl Acad Sci USA 2012 109 15673 (f) Tamaki Y Koike K Morimoto T

Ishitani O J Cat 2013 135 22 (g) Tamaki Y Koike K Morimoto T Yamazaki Y

Ishitani O Inorg Chem 2013 52 11902

26

IL3

A PARADIGM FOR THE PRACTICAL AND ECONOMICAL FORMATION

OF CARBONmdashCARBON AND CARBONmdashHETEROATOM BONDS

ORGANOCATALYTIC REDOX COUPLED TRANSITION METAL

CATALYZED DEHYDRATIVE BOND CONSTRUCTIONS

LS Liebeskind MG Lindale

Emory University Department of Chemistry Atlanta Georgia USA

The current world-wide focus on C-H functionalization is driven in part by the conceptual promise

of atom-efficient sustainable syntheses from readily available feedstocks Of equal conceptual

value is the dehydrative formation of CmdashC CmdashN and CmdashO bonds from common bioavailable

hydroxylic reactants like carboxylic acids alcohols and phenols Given the sustainable generation

of hydroxylic feedstocks dehydrative bond formations can impact all levels of synthesis

(commodities fine chemicals biologicals) if they are efficient economical practical and substrate

general And they are uniquely poised to contribute to the search for the sustainable conversion of

biomass to biofuels This lecture describes a paradigm for the conversion of hydroxylic reactants to

value-added CmdashC CmdashN and CmdashO products based on a practical organocatalytic redox-coupled

transition metal catalyzed dehydrative bond forming process

27

IL4

CHEMICAL SYNTHESIS USING AMPHOTERIC MOLECULES

AK Yudin

University of Toronto

Over the past seven years my lab has been exploring the use of amphoteric molecules in chemical

synthesis What started as a curiosity-driven project has turned into a sustained exploration of a

virtually untouched segment of chemistry characterized by molecules with unusual combinations of

functional groups The multifunctional nature arising from forced orthogonality enables amphoteric

molecules to participate in reactions of high atom- and step- economy thereby enabling efficient

syntheses characterized by minimal reliance on protecting groups

In this lecture I will illuminate several classes of reagents developed in our lab I will discuss the

discovery of bench-stable aldehydes equipped with a C-B bond at the alpha position These

intriguing molecules have enabled the synthesis of a rich palette of other reagents that contain

carbon-boron bonds at strategic positions With the growing repertoire of boron-containing

amphoteric molecules we are in a good position to explore ideas that range from reaction discovery

to the synthesis of boron-based biologically active compounds

I will also present the evolution of peptide macrocyclization technology driven by amphoteric

aziridine aldehydes As part of this study we are attempting to understand the conformational

preferences of peptide macrocycles As a result we are moving closer to our ultimate goal of

rationalizing the behavior of a wide range of substrate classes in our cyclization reactions as well as

understanding cellular activity of macrocycles I will conclude my talk with a discussion of our

integrative macrocyclization approaches and will present recent results of our protein crystallization

efforts

28

IL5

EMERGENT FUNCTION FROM COMPLEX ADAPTIVE CATALYSTS

VV Fokin

The Scripps Research Institute Department of Chemistry La Jolla California USA and Moscow

Institute of Physics and Technology Dolgoprudny Russia

Exploiting the versatility of catalytic processes requires rigorous interrogation of the constantly

changing environment of the catalyst Detailed understanding of critical events affecting a catalyst

such as activation and deactivation unproductive off-cycle pathways and changes in the nature of

dominant species are of critical importance The seemingly formidable challenge of controlling the

reactivity of complex catalytic systems that involve dynamic and rapidly equilibrating mixtures of

intermediates may in fact be their advantage well-defined (ie non-adaptable) catalysts are often

inefficient when compatibility with many functional groups and conditions is the goal

Examples of investigation of such catalytic reactions will be illustrated by case studies of transition

metal-catalyzed transformations of alkynes Alkynes are among the most energetic hydrocarbons

and transition metals enable selective and controlled manipulation of the triple bond revealing their

unique reactivity transformations of alkynes into heterocycles and into a variety of molecules with

new carbonndashheteroatom bonds These seemingly simple transformations involve an impressive

variety of intermediates yet proceed with high selectivity and efficiency maintaining their reactivity

in most complex environments such as the biological milieu of living organisms

29

IL6

RAPID PHOTOASSISTED ACCESS TO sp3-RICH POLYHETEROCYCLIC

SCAFFOLDS

OA Mukhina NNB Kumar WC Cronk WJ Umstead AG Kutateladze

Department of Chemistry and Biochemistry University of Denver USA

Photochemical reactions hold unparalleled promise for building prohibitively strained carbo‐ and

heterocyclic scaffolds which offer expeditious access to difficult synthetic targets not accessible via

ground state chemistry Yet photochemistry is underutilized by the synthetic community which is

especially true for Diversity Oriented Synthesis (DOS) In this context we have been developing a

new photoassisted synthetic methodology which will enhance synthetic chemistry toolbox and will

be compatible with DOS1 This new photoassisted synthetic methodology allows for rapid access

to topologically diverse polycyclic scaffolds decorated by various functional groups and

carboheterocyclic pendants rigidly or semi-rigidly held in a unique spatial configuration by these

novel core frameworks Access to such topologically diverse scaffolds is realized via key

photochemical steps and their combination with ground state reactions most prominently via the

recently discovered intramolecular cycloaddition reactions of azaxylylenes and quinomethanes

photogenerated via excited state intramolecular proton transfer Details of an experimental and

theoretical mechanistic study to gain deeper understanding of underlying processes in the excited

states will also be discussed

A typical example of rapid growth of complexity in a photoassisted synthesis of enantiopure

conformationally locked ribofuranosylamines spiro-linked to oxazolidino-diketopiperazines via a

straightforward ldquoassemblyrdquo of a threonine-based photoprecursor photochemical transformation

and a simple post-photochemical modification is shown below

[1] (a) Mukhina OA Kumar NNB Arisco TM Valiulin RA Metzel GA Kutateladze

AG Angew Chem Int Ed 2011 50 9423-9428 (b) Nandurkar NS Kumar NNB

Mukhina OA Kutateladze AG ACS Combinatorial Sci 2013 15 73-76 (c) Kumar

NNB Mukhina OA Kutateladze AG J Am Chem Soc 2013 135 9608-9611 (d)

Cronk WC Mukhina OA Kutateladze AG J Org Chem 2014 791235-1246

30

IL7

TRANSITION METAL CLUSTERS UNAVOIDABLE CONTAMINANTS OR

IMPORTANT PLAYERS IN SOLUTION

VP Ananikov

Zelinsky Institute of Organic Chemistry Russian Academy of Sciences Leninsky Prospect 47

Moscow 119991 Russia Department of Chemistry Saint Petersburg State University Stary

Petergof 198504 Russia

Application of transition metal catalysis in organic synthesis is an area of outstanding progress with

prominent achievements in carbon-carbon cross-coupling carbon-heteroatom bond formation and

atom-economic construction of organic molecules

Mechanistic studies have revealed two different frameworks for catalytic processes in solution

depending on the nature of selected system and on the type of catalyst precursor used single type

metal species catalysis or multiple metal species catalysis [1] The first type of systems is widely

utilized and it is based on well-defined metal complex with strongly bound ligands The catalyst

precursor undergoes only partial or minor chemical modifications prior entering the catalytic cycle

In this model the formation of other metal derivatives is not facilitated and the active core of the

catalyst is preserved throughout the catalytic cycle

The second model can be considered as multiple metal species catalysis (in some cases - ldquococktailrdquo

of catalysts) and involves a range of simultaneously present and dynamically interchangeable metal-

containing species such as metal complexes clusters and nanoparticles [2] Such mechanistic

picture may be expected when in situ generated catalysts are employed or upon usage of

nanoparticles as catalysts precursors

It is of much interest to reveal the role of metal clusters in these catalytic systems Formation of

clusters was detected in many cases although their role remains unclear In some cases the presence

of clusters was related to decomposition of the active form while in the other cases the formation of

dinuclear and polynuclear species is an important stage of catalyst evolution in solution

We have investigated soluble metal complexes and nanoparticles of Pd Ni Pt and Au for

development of efficient catalytic systems for selective carbon-heteroatom and carbon-carbon bond

formation in solution [3-5] Homogeneous transition-metal-catalyzed reactions and heterogeneous

nanoparticle-catalyzed reactions were considered with a focus on metal species interconversions

and nanoparticle contamination of homogeneous catalytic systems

References

[1] Kashin AS Ananikov V P J Org Chem 2013 78 11117 (doi 101021jo402038p)

[2] Ananikov V P Beletskaya I P Organometallics 2012 31 1595 (doi 101021om201120n)

[3] Zalesskiy S S Sedykh A E Kashin A S Ananikov V P J Am Chem Soc 2013 135

3550 (doi 101021ja311258e)

[4] Ananikov V P Orlov N V Zalesskiy S S Beletskaya I P Khrustalev V N Morokuma

K Musaev D G J Am Chem Soc 2012 134 6637 (doi 101021ja210596w)

[5] Kashin A S Ananikov V P Top Catal 2013 56 1246 (doi 101007s11244-013-0091-5)

31

IL8

SIMPLE COPPER CATALYSTS FOR C-C C-N AND C-O BONDS

FORMATION

F Monnier

Institut Charles Gerhardt (UMR 5253) ENSCM FRANCE

Since its renaissance in 2001 [1] the copper cross-coupling of nucleophiles with aryl halides has

been increasingly studied [2] In this account we exposed our last contribution for the formation of

C-C [3] C-N [4] and C-O [5] bonds catalyzed by a cheap and simple combination of copper salts

and -diketone ligands

1 a) M Taillefer H-J Cristau P P Cellier J-FSpindler Env SAU2001-1009 and SAU2001-

01044 patents Fr2833947-WO0353225 (Pr Nb Fr 2001 16547) M Taillefer H-J Cristau P

P Cellier J-F Spindler A Ouali Fr2840303-WO03101966 (Pr Nb Fr 2002 06717) b) S L

Buchwald A Klapars J C Antilla G E Job M Wolter F Y Kwong G Nordmann E J

HennessyWO02085838 (priority number US0286268 2001)

2 For a review see F Monnier M Taillefer Angew Chem Int Ed 2009 48 6954-697

3 a) G Danoun A Tlili F Monnier M Taillefer Angew Chem Int Ed 2012 51 12815 b)

MTaillefer F Monnier A Tlili G Danoun PCT Int Appl (2013) WO 2013 EP61697

20130606 FR20120055275 20120606

4 a) A Tlili F Monnier M Taillefer Chem Commun 2012 48 6408-6410 b) E Racine F

Monnier J-P Vors M Taillefer Chem Commun 2013 49 7412 c) E Racine F Monnier J-

P Vors M Taillefer Org Lett 2011 13 2818

5 a) A Tlili N Xia F Monnier M Taillefer Angew Chem Int Ed 2009 48 8725-8728

32

IL9

INTERACTIONS IN IONIC LIQUIDS PROBED BY NMR SPECTROSCOPY

DISTANCES CONFORMATIONS AND MORE

R Giernoth A Broehl Y Lingscheid

University of Cologne Department of Chemistry Koeln Germany

One often-mentioned aspect of ionic liquids (ILs) is that they are ldquodesigner solventsldquo whose

properties can be designed for any particular need [1] Obviously it is impossible to choose a

different property for a given IL but only a different IL entirely To be able to sensibly do so it is

necessary to know about the supramolecular structures and the governing interactions in the ionic

liquid phase

NMR spectroscopy and the nuclear overhauser effect

spectroscopy (NOE) in particular is the method of choice

for the investigation of ion pair interactions [2] The

NOE arises due to inter- and intramolecular cross

relaxation

To be able to precisely measure interactions in solution

an internal distance standard is needed We have

synthesized a monofluorinated ionic liquid which was subsequently employed in NOE-based NMR

investigations for the determination of distances and interactions in the ionic liquid phase

In a different project we are studying the influence of

different ionic liquids on peptide conformations much

in accord with the well-known Hofmeister series of ions

[3] With the help of a model system we are going to

demonstrate that the choice of ions has a strong effect on

the tertiary structure of different peptides in solution

and how these effects can be used for new non-native

peptide chemistry

References

[1] for reviews see JP Hallett T Welton Chem Rev 2011 111 3508-3576 E J Maginn J

Phys Condens Matter 2009 21 1ndash17

[2] P S Pregosin Pure Appl Chem 2009 81(4) 615ndash633 Y Lingscheid S Arenz R Giernoth

ChemPhysChem 2012 13 261ndash266

[3] F Hofmeister Arch Exp Pathol Pharmakol 1888 64 247

33

IL10

APPLICATION OF α-CF3-SUBSTITUTED DIAZOCOMPOUNDS IN

ORGANIC SYNTHESIS AND CATALYSIS

SN Osipov DV Vorobyeva IE Tsishchuk

AN Nesmeyanov Institute of Organoelement Compounds Russian Academy of Sciences Moscow

An efficient pathway to multifunctional CF3-containing aromatic heteroaromatic and heterocyclic

compounds including cyclic amino carboxylic and amino phosphonic acid derivatives have been

developed The method is based on in situ generation of highly electrophilic CF3-carbene species

from the corresponding α-diazo carboxylates or phosphonates under Cu- or Rh-catalysis and their

reactions with appropriate nucleophilic partners1-4

The further applications of the reaction products in metal-catalysed transformations of different

types eg such as ring closing diene and ene-yne metathesis intramolecular Pauson-Khand

reaction as well as [2+2]-cycloaddition open an access to new families of fluorinated molecules

References

1 DV Vorobyeva AK Mailyan AS Peregudov NM Karimova TP Vasilyeva IS

Bushmarinov C Bruneau PH Dixneuf SN Osipov Tetrahedron 2011 67 3524

2 AK Mailyan IM Krylov C Bruneau PH Dixneuf SN Osipov Synlett 2011 2321

3 AK Mailyan IM Krylov C Bruneau PH Dixneuf SN Osipov Eur J Org Chem

2013 5353

4 IE Tsishchuk DV Vorobyeva AS Peregudov SN Osipov Eur J Org Chem 2014

2480

34

IL11

NEW ADVANCES IN ORGANOMETALLIC AND PHOSPHORUS

ELECTROCHEMISTRY

DG Yakhvarov OG Sinyashin

AEArbuzov Institute of Organic and Physical Chemistry Laboratory of Organometallic and

Coordination Compounds Kazan Russian Federation

The development of modern chemical science and creation of new industrially applicable

technologies are focused on application of effective and ecologically safe methods for the

preparation of important and useful chemical compounds and materials The combination of

transition-metal catalysis and organic electrosynthesis has attracted increasing attention due to the

high selectivity and efficiency of this approach in the synthetic preparation of various compounds

bearing carbon-carbon and carbon-element bonds The mild conditions single-stage process cyclic

regeneration of the catalyst and convenient and relatively inexpensive form of the energy used are

the main advantages of electrochemical methods Application of electrochemical processes to large-

scale production (macroscale synthesis) has led to significant development of the chemical

technologies of the 21st century due to easy access to highly reactive intermediates and tuning of

the reactivity of the substrate used during the synthetic process by simple adjustment of the

electrode potential

The elaborated in our research group electrochemical methods have been successfully applied for

generation of organometallic sigma-complexes1 which are important intermediates of different

carbon-carbon and carbon-element coupling processes selective preparation of organophosphorus

compounds from white phosphorus2 activation of inert oligophosphorus moieties formed in the

coordination sphere of transition metal complexes3 selective cleavage of the tungsten-phosphorus

bond resulting in valuable metal-free phosphorus heterocycles obtained via phosphinidene

intermediates4

Herein we present recent advances in synthetic application of the electrochemical techniques for

preparation and activation of organonickel complexes1 and generation of new previously known as

unstable phosphorus intermediates5 which can be applied for preparation of practically useful

organophosphorus compounds transition metal catalysts and magnetically active materials6

Acknowledgements Financial support from the Russian Scientific Fund (project 14-13-01122) and

Russian Foundation for Basic Research (project 09-03-00933-a) is gratefully acknowledged

References

[1] DGYakhvarov AFKhusnuriyalova OGSinyashin Organometallics 2014 in press

[2] DGYakhvarov EVGorbachuk OGSinyashin Eur JInorgChem 2013 4709

[3] DYakhvarov PBarbaro LGonsalvi SMantildeas SMidollini AOrlandini MPeruzzini

OSinyashin FZanobini Angew Chem Int Ed 2006 45 4182

[4] DGYakhvarov YuHBudnikova NHTran Huy LRicard FMathey Organometallics

2004 23 1961

[5] DYakhvarov MCaporali LGonsalvi ShLatypov VMirabello IRizvanov OSinyashin

PStoppioni MPeruzzini Angew ChemIntEd 2011 50 5370

[6] DYakhvarov ETrofimova OSinyashin OKataeva PLoumlnnecke EHey-Hawkins APetr

YuKrupskaya VKataev RKlingeler BBuumlchner Inorg Chem 2011 50 4553

35

IL12

TRIFLUOROMETHYLATION BY SUNLIGHT-PROMOTED

PHOTOREDOX CATALYSIS

T Koike M Akita

Tokyo Institute of Technology Chemical Resources Laboratory Yokohama Japan

Photoredox catalysis 1 mediated by photo-sensitizers (eg [Ru(bipy)3]

2+ and relevant Ir complexes)

has attracted increasing attention as practical green synthetic chemical processes because they are

visible light-promoted redox-neutral reactions

We have demonstrated that photoredox catalysis is a powerful synthetic tool in particular for

trifluoromethylation of olefinic substrates which is the topic of the presentation23

In all cases

electron transfer from the photoexcited metal species to an electrophilic CF3-reagent generates the

key CF3 radical intermediate together with the cationic species of the catalyst Subsequent

addition of the CF3 radical to the olefinic substrate followed by oxidation of the resultant carbon

radical intermediate by the cationic metal species gives the carbocationic intermediate which is

trapped by nucleophiles or deprotonated to furnish the coupling products The sequential redox

processes make the system redox-neutral It is remarkable that the reactions are promoted not only

by artificial light sources (eg Xe lamp and blue LED lamps) but also by sunlight

References 1) C K Prier D A Rankic and D W C MacMillan Chem Rev 113 5322 (2013)

2) T Koike and M Akita (a) Synlett 24 2492 (2013) (b) Topics in Cat 259 in press (2014)

(DOI 101007s11244-014-0259-7) 3) Y Yasu T Koike M Akita et al (a) Angew Chem Int

Ed 51 9567 (2012) (b) Chem Commun 49 2037 (2013) (c) Org Lett 15 2136 (2013) (d)

Org Lett 16 in press (2014) (DOI 101021ol403500y) (e) Beilstein J Org Chem submitted

(f) to be submitted see also (g) Chem Commun 48 5355 (2012) (h) ibid 49 7249 (2013)

36

IL13

CYCLIC HYPERVALENT IODINE REAGENTS A TREASURE OF

REACTIVITY FOR CATALYSIS AND SYNTHESIS

J Waser

Ecole Polytechnique Federale de Lausanne ISIC SB LCSO Lausanne Switzerland

The non-classical four electrons three centers bonds of hypervalent iodine are weaker than normal

classical bonds This confers an exceptional reactivity to these compounds as oxidants or atom-

transfer reagents Cyclic hypervalent iodine reagents are especially interesting as they combine

enhanced stability with unique opportunities for reactivity modulation In particular our group has

been interested in the development of alkynylation methods using cyclic EthynylBenziodoXolone

(EBX) hypervalent iodine reagents1 Interesting recent results of our research in the area includes

the first example of gold-catalyzed domino cyclization-alkynylation2 and a highly efficient and

practical alkynylation method for thiols3 Herein we will present our most recent work in the area

of electrophilic alkynylation as well as the extension of the use of cyclic hypervalent iodine

reagents to other functionalization reactions

References

1 JP Brand J Waser Chem Soc Rev 2012 41 4165-4179

2 Y Li J P Brand J Waser Angew Chem Int Ed 2013 52 6743-6747

3 R Frei J Waser J Am Chem Soc 2013 135 9620-9623

37

IL14

THEORY AND COMPUTATION PROVIDE INSIGHTS AND DISCOVERY

ON CHEMICAL REACTIONS OF COMPLEX MOLECULAR SYSTEMS

K Morokuma12

1 - Fukui Institute for Fundamental Chemistry Kyoto University Kyoto Japan

2 - Cherry L Emerson Center for Scientific Computation and Department of Chemistry Emory

University Atlanta GA USA

The chemical reaction that creates destroys reorganizes chemical bonds to produce new

compounds is the most important subject of chemistry Theoreticalcomputational studies have

come a long way and are now playing the central role in providing insights in understanding the

mechanism and dynamics of chemical reactions as well as in discovery of new reaction mechanisms

and reaction systems The theory can study not only the reaction of the ground state of molecules in

gas phase but also reactions of excited electronic states as well complicated reactions of complex

molecular systems The information theoreticalcomputational studies can provide is often

complementary to the information experimental studies provide and research on chemical reactions

is becoming impossible without strong collaboration between theorists and experimentalists

In the present talk I will discuss some of our recent studies of chemical reactions We have

developed the Global Reaction Route Mapping (GRRM) strategy for automatic exploration of

reaction pathways of complex molecular systems The ADDF (anharmonic downward distortion

following) and the AFIR (artificial force induced reaction) methods in the GRRM strategy have

been used for determination of not only energy minima and saddle points on the potential energy

hypersurfaces but also minima and saddle points on the conical intersection and crossing seam

hypersurfaces I will discuss the GRRM strategy and applications to several reaction systems

including photodissociation reactions catalytic reactions and enzymatic reactions

38

IL15

COMPUTATIONAL INSIGHTS INTO C-H FUNCTIONALIZATION

JUNGLE

D Musaev

Cherry L Emerson Center for Scientific Computation Emory University Atlanta Georgia USA

I will present our integrated and

collaborative approaches to the

Transition metal catalyzed C-H bond

functionalization I will elaborate our

efforts on understanding the transition

metal catalyzed C-H bond alkylation

and amination reactions and analyze

the factors controlling the reactivity of

these reactions and make intriguing

predictions I will discuss our latest

results [1] on the mono-protected amino acid ligands (MPAA) promoted Pd(II)-catalyzed

enantioselective CndashH activation reactions The presented computation allowed us to gain insights

into the mechanisms nature of active species a ligand coordination mode to the Pd(II) and

transition state structure of the CndashH activation step Our findings were supported by experiments

[1] D G Musaev T M Figg and A L Kaledin Chem Soc Rev DOI 101039C3CS60447K

(2014)

PR3

Ar

Pd

I

Ph

CsF

HCsPd

RZ ZR

Pd

ZRZR

ZR

Pd

ZR

Pd

RZ ZR

Pd

ZR

ZR

ZR ZRPd

Active

Inactive

Cs2-I-F assisted

PdNO

N

O

PG

H Ph

H

i-Pr

H

O

-

O

Ligand accelerated

Protecting Group effectBase (Cs)-effectPd-cluster effect

C-H FUNCTIONALIZATION

DIRECT Ar-Ar COUPLING

SELECTIVE RSHRSeH + C C

Pd(II)- PRECATALYST

39

IL16

A NOVEL TRIFLUOROMETHANESULFONYL HYPERVALENT

IODONIUM YLIDE FOR TRIFLUOROMETHYLTHIOLATION

N Shibata

Nagoya Institute of Technology Department of Nanopharmaceutical Sciences Nagoya Japan

In the last few decades numerous methods for the introduction of a trifluoromethylthio group into

organic compounds have been developed The main strategies are indirect methods including

halogen-fluorine exchange and trifluoromethylation of sulfur-containing compounds such as

disulfides thiols and thiolates Obviously the most attractive and ideal route to constitute the CF3S

moiety is the direct introduction of this functional group However in this approach some

limitations are usually encountered including the use of gaseous and highly toxic reagents such as

CF3SCl or unstable reagents and the modest scope of substrates Although several transition

metal-mediated or catalyzed trifluoromethylthiolation methods have been developed the substrates

are mostly limited to aromatic compounds Recently Billard and co-workers reported that

trifluoromethanesulfanylamides were effective for trifluoromethylthiolation of alkenes alkynes

indoles and organometallic species More recently Lu and Shen also developed a novel hypervalent

iodine reagent for the trifuoromethylthiolation of aryl and vinyl boronic derivatives alkynes and β-

ketoesters Even though these direct trifluoromethylthiolation reagents are shelf-stable a more

critical issue is the fact that these CF3S regents should be prepared in advance by

trifluoromethylthiolations or related trifluoromethylations Due to these limitations and negative

aspects it is thus still necessary to develop an efficient and easily available reagent to introduce the

CF3S moiety directly In contrast to the CF3S unit a trifluoromethanesulfonyl (CF3SO2) unit is

stable and often found in commonly used organic reagents such as CF3SO2Cl CF3SO2Na CF3SO2H

and (CF3SO2)2 In this context we came up with a novel idea of using ubiquitous CF3SO2

compounds as reagents for introducing the CF3S unit under reductive conditions As a part of our

recent work on the chemistry of trifluoromethanesulfonyl compounds (triflones) we herein disclose

a novel trifluoromethanesulfonyl hypervalent iodonium ylide as a shelf-stable reagent for

electrophilic-type trifluoromethylthiolation A wide variety of nucleophiles are nicely converted

into the corresponding trifluoromethylsulfanyl products by this reagent

Reference Y-D Yang A Azuma E Tokunaga M Yamasaki M Shiro N Shibata J Am

Chem Soc 135 8782 (2013)

40

IL17

CATALYSIS-ASSISTED SIGNAL ENHANCEMENT IN NUCLEAR

MAGNETIC RESONANCE

IV Koptyug

International Tomography Center SB RAS Novosibirsk Russia

When parahydrogen (nuclear spin isomer of H2) is used in catalytic hydrogenations instead of

normal H2 the NMR signals of reaction products and intermediates can be enhanced by 3-4 orders

of magnitude and more owing to the phenomenon of parahydrogen-induced polarization (PHIP)

This possibility has been explored previously in the context of activation of H2 by transition metal

complexes and clusters in solution It has been shown that PHIP can help to detect reaction products

and short-lived intermediates not detectable by conventional NMR As most of the industrial

catalytic processes are heterogeneous it would be desirable to employ PHIP in the NMR studies of

heterogeneous catalysts and catalytic reactions The objective of our research is thus to extend the

scope of PHIP applications to the heterogeneously (HET) catalyzed hydrogenation reactions and to

develop a hypersensitive NMR-based technique for the in situ and operando studies of

heterogeneous catalytic processes In addition HET-PHIP can be employed to produce catalyst-free

hyperpolarized liquids and gases for novel MRI applications including the advanced in vivo studies

We demonstrate that similar to their homogeneous counterparts heterogenized transition metal

complexes are able to produce strong NMR signal enhancements when parahydrogen is used in the

hydrogenation reactions [1] Our recent results show that various immobilized metal complexes are

can produce HET-PHIP both in liquid phase and in gas phase hydrogenations In contrast for

supported metal catalysts (eg PtAl2O3) dissociative hydrogen chemisorption and rapid migration

of H atoms on the metal surface were expected to make the required pairwise hydrogen addition to

a substrate molecule impossible Nevertheless we have shown that PHIP can be successfully

observed both in liquid-solid and in gas-solid heterogeneous hydrogenations catalyzed by supported

metal catalysts [1] The NMR signal enhancement was found to be sensitive to the metal

nanoparticle size and shape the nature of the metal and support and the type of substrate used in

the reaction Recently HET-PHIP effects were also demonstrated for several metal oxides and bulk

unsupported metals used as hydrogenation catalysts [2] The implications of these results for the

mechanisms of heterogeneous hydrogenation processes are discussed [13] Further potential

extensions of the technique will be presented including the use of metal-free catalysts for activating

parahydrogen [4] and the prospects of using nuclear spin isomers of molecules other than H2 to

further extend the range of reactions and processes that can be explored in detail using the PHIP

technique [5] In addition to applying HET-PHIP to the mechanistic and kinetic studies of

heterogeneous hydrogenations several MRI applications of HET-PHIP have been already

demonstrated including MR imaging of a catalytic reaction in an operating model microreactor [6]

1 KV Kovtunov VV Zhivonitko IV Skovpin DA Barskiy IV Koptyug Top Curr Chem 338 123

(2013)

2 KV Kovtunov DA Barskiy OG Salnikov AK Khudorozhkov VI Bukhtiyarov IP Prosvirin IV

Koptyug Chem Commun 50 875 (2014)

3 OG Salnikov KV Kovtunov DA Barskiy AK Khudorozhkov EA Inozemtseva IP Prosvirin VI

Bukhtiyarov IV Koptyug ACS Catal 4 2022 (2014)

4 VV Zhivonitko V-V Telkki K Chernichenko TJ Repo M Leskela V Sumerin IV Koptyug J

Amer Chem Soc 136 598 (2014)

5 VV Zhivonitko KV Kovtunov PL Chapovsky IV Koptyug Angew Chem Int Ed 52 13251

(2013)

6 VV Zhivonitko V-V Telkki IV Koptyug Angew Chem Int Ed 51 8054 (2012)

41

IL18

-BOND ACTIVATION REACTION BY TRANSITION METAL AND MAIN-

GROUP ELEMENT COMPOUNDS AND CATALYTIC REACTION

INCLUDING IT

S Sakaki

Fukui Institute for Fundamental Chemistry Kyoto University Takano Sakyo-ku Kyoto 606-8103

Japan

The -bond activation by transition metal complexes attracts a lot of interests in theoretical and

organometallic chemistries because it is crucial in many catalytic reactions by transition metal

complexes In our understanding -bond activation is classified to two categories the concerted

oxidative addition to M (metal) the stepwise oxidative addition via nucleophilic attack the

oxidative addition to M-L (L = neutral ligand) and the heterolytic activation by M-X (X = anionic

ligand) activation by metal center only and that by the metal-ligand moiety12

MLn + R1-R2 cis-MLn(R1)(R

2) (1)

MLn + R1-X [MLn(R1)] --(X) trans-MX(R

1)Ln (2)

MLLn + R1-R2 MLn(R1)(L-R

2) (3)

MXLn + R1-R2 MLn(R1) + R

2-X (4)

We theoretically investigated these reactions and elucidated the characteristic electronic processes

and clear understanding2 We also theoretically investigated catalytic reactions including -bond

activation In this talk we wish to present our recent theoretical studies of carboxylation of

phenylchloride catalysed by a nickel(0) complex hydrosilylation of carbon dioxide catalyzed by

germanium(II)- and zinc(II)-hydride compounds3

In my talk I wish to present comprehensive understanding of these -bond activation reactions and

the importance of -bond activation reaction in such catalytic reactions as CO2 conversion and

cross-coupling reactions

References

1 S Sakaki Y-y Ohnishi H Sato Chem Record 10 29 (2010) W Guan F B Saeed S

Sakaki Inorg Chem in press

2 N Ochi Y Nakao H Sato S Sakaki J Am Chem Soc 129 8615 (2007) N Ochi Y Nakao

H Sato S Sakaki J Phys Chem A 114 659 (2010)

3 N Takagi and S Sakaki J Am Chem Soc 135 8955 (2013) M Deschmukh to be submitted

42

IL19

NONPLANAR HETEROAROMATICS SYNTHESIS AND SELF-ASSEMBLY

M Stepien

Wydziaі Chemii Uniwersytet Wrocіawski

Even though π-electron aromaticity is typically associated with planar structures several classes of

distorted π-aromatics are known including a variety of twisted helical bowl-shaped or tubular

systems Such distortions are of fundamental interest because they provide a means of testing

different aspects of aromaticity theory but they also may have practical consequences as a

potential method of fine-tuning the electronic structure and self-assembly properties of aromatic

compounds

In this contribution two synthetic approaches to nonplanar heteroaromatics will be discussed One

is based on oxidative coupling reactions of pyrrole-containing precursors and is exemplified by our

recent syntheses of peripherally fused porphyrin derivatives1 (1 and 2) and bipyrroles

2 Compounds

1ndash2 are characterized by bathochromically shifted electronic absorptions and very high extinction

coefficients Phenanthroporphyrins 1 and their complexes reveal substitution-dependent aggregation

in solution and form columnar mesophases in the condensed phase The zinc(II) complex of

benzochrysenoporphyrin 2 was found to form a unique 3D-ordered mesophase containing discrete

multiporphyrin aggregates

The other approach to nonplanar aromatics explored in our laboratory which is suitable to the

synthesis of bowl- or belt-shaped structures involves the so-called fold-in synthesis3 performed on

appropriately designed macrocyclic precursors The fold-in concept can be realized using different

reactivity types including Ullmann-type reductive coupling as in the recent synthesis of

chrysaorole (3)34

and FriedelndashCrafts alkylation5

(1) Myśliwiec D Donnio B Chmielewski P J Heinrich B Stępień M J Am Chem Soc

2012 134 4822ndash4833

(2) Gońka E Myśliwiec D Lis T Chmielewski P J Stępień M J Org Chem 2013 78

1260ndash1265

(3) Stępień M Synlett 2013 24 1316ndash1321

(4) Myśliwiec D Stępień M Angew Chem Int Ed 2013 52 1713ndash1717

(5) Kondratowicz M Myśliwiec D Lis T Stępień M in preparation

43

IL20

RHODIUM N-HETEROCYCLIC CARBENE COMPLEXES AS EFFICIENT

CATALYSTS FOR X-H ADDITIONS TO ALKYNES THE QUEST FOR

SELECTIVITY

R Castarlenas A Di Giuseppe L Rubio-Perez L Palacios R Azpiroz V Polo JJ Perez-

Torrente LA Oro

ISQCH Universidad de Zaraaragoza-CSIC

The development of new catalytic systems for the synthesis of added-value products in a selective

manner and with high atom economy is nowadays an important task In this context our group has

recently prepared new rhodium complexes bearing an N-heterocyclic carbene (NHC) ligand that

have been disclosed to be very active and gem-selective for X-H additions across C-C triple

bonds1-4

Experimental and theoretical (DFT) mechanistic studies indicate that the presence of a

bulky powerful electron-releasing NHC and the rational choice of the auxiliary ligands is essential

in order to control the selectivity towards the formation of Markonikov-type products

1 A Di Giuseppe R Castarlenas JJ Perez-Torrente M Crucianelli V Polo R Sancho FJ

Lahoz LA Oro J Am Chem Soc 2012 134 8171

2 L Palacios MJ Artigas V Polo FJ Lahoz R Castarlenas JJ Perez-Torrente LA Oro ACS

Catal 2013 3 2910

3 L Rubio-Peacuterez R Azpiacuteroz A Di Giuseppe V Polo R Castarlenas JJ Perez-Torrente LA

Oro Chem Eur J 2013 19 15304

4 R Azpiacuteroz A Di Giuseppe R Castarlenas JJ Perez-Torrente LA Oro Chem Eur J 2013

19 3812

44

IL21

CATALYTIC OLEFINATION REACTION ndash UNIVERSAL METHOD FOR

SYNTHESIS OF ALKENES

VG Nenajdenko

Moscow State University Department of Chemistry Leninskie Gory Moscow 119992

Catalytic olefination reaction represents new approach to the preparation of double C=C bond N-

unsubstituted hydrazones can be converted into alkenes by treatment with polyhalogenated alkanes

in presence of a base and catalytic amounts of copper salts The reaction has a wide synthetic scope

allowing to prepare both alkyl and aryl halogenoalkenes including fluorinated ones and derivatives

with functional groups Simple experimental procedure which does not require using of

organometallic or toxic organophospourous compounds affordable price and availability of starting

materials high yields and stereoselectivity are distinct advantages of the reaction

R2

R1

COOR

Cl

R2

R1

Cl

CN

R2

R1

F

F

O

R2

R1

R2

R1

Cl

Cl

R2

R1

Br

Br

R2

R1

CH2OH

Cl

R2

R1

CClF2

F

R2

R1

CF3

Cl

R2

R1

Cl

F

R2

R1

CBrF2

F

CBrF2R

R2

R1

CBrF2

F

F

R2

R1

CONR2

Cl

R2

R1

Cl

O

O

R2

R1

I

H

R2

R1

Cl

H

R2

R1

Br

H

45

IL22

HOW TO MAKE COMPLEX MOLECULES FROM SIMPLE STARTING

MATERIAL THE PALLADIUM A POWERFUL TOOL

J Suffert

University of StrasbourgCNRS

In addition to molecular complexity the challenge of the chemist today is also the quest for

efficiency of the synthetic route and maximization of structural complexity Our laboratory

investigations focus for several years on the study of an unprecedented cascade reaction involving a

rare 4-exo-dig cyclocarbopalladation followed by a terminated cross-coupling with an

organometallic reagent A 6 - or 8 -electrocyclization can occur leading to new tricyclic structures

The seminar will show that we can offer an easy access to complex polycyclic molecules resulting

from readily available simple starting materials Eventually it will be possible to propose the

elaboration of a large collection of unprecedented structurally novel molecules based on recent

promising results Below are represented several complex structures that has been prepared through

the powerful 4-exo-dig cyclocarbopalladation Many other extension of this method have not been

so far explored and can afford a multitude of new and original scaffolds

46

IL23

SYNTHESIS OF TIN AND LEAD ANALOGS OF CYCLOPENTADIENYL

ANION AND THEIR APPLICATION TO TRANSITION-METAL

COMPLEXES

M Saito

Department of Chemistry Graduate School of Science and Engineering Saitama University

Shimo-okubo Sakura-ku Saitama-city Saitama 338-8570 Japan

We succeeded in the generation of tetraphenyldilithiostannole 1a[1]

and its considerable aromatic

character was established by X-ray diffraction analysis and theoretical calculations[2]

The lead

analog tetraphenyldilithioplumbole 2 was also found to be aromatic indicating that the concept of

aromaticity is expanded to lead-bearing carbon cycles[3]

After the synthesis of heavier congeners of Cp anion attention was next paid to the preparation of

transition-metal complexes with such heavier Cp ligands The first heavier metallocene was a

ruthenocene bearing a germole ligand[4]

and transition-metal complexes with silole and germole

ligands have already been synthesized The straightforward method for the synthesis of such

metallocenes is the reactions of metallole anions and dianions with transition-metal reagents

However the reactions using stannole anions and dianions had never been reported until recently

We examined the reaction of tetraphenyldilithiostannole 1b[5]

with [CpRuCl]4 and butterfly

complex 3 was obtained instead of an expected ruthenocene[6]

The reaction of 1b with Cp2TiCl2

afforded three-membered ring compound 4 with unique electronic states[7]

The synthesis of the first

neutral triple-decker complex 5 with group 14 metallole ligands was also achieved using silyl-

substituted dilithiostannole 1c

M

R2

R2

R1

R1

L i

L i

M = S n R1

= R2

= P h

M = S n R1

= R2

= E t

M = S n R1

= M e 3S i R2

= P h

M = P b R1

= R2

= P h

1 a

1b

1c

2

R u

R u

S n S n

E tE t

E t

E t

E t

E t

E t

E t

C p

C p

3

T i

S n

S nC p

C p

4

S n

S iM e 3

M e 3S i

P h

P h

R u C p C p R u

5

References

[1] Saito M Haga R Yoshioka M Chem Commun 2002 1002

[2] Saito M Haga R Yoshioka M Ishimura K Nagase S Angew Chem Int Ed 2005 44

6553

[3] Saito M Sakaguchi M Tajima T Ishimura K Nagase S Hada M Science 2010 328

339

[4] Freeman W P Tilley T D Rheingold A L Ostrander R L Angew Chem Int Ed Engl

1993 32 1744

[5] Saito M Kuwabara T Kambayashi C Yoshioka M Ishimura K Nagase S Chem Lett

2010 39 700

[6] Kuwabara T Saito M Guo J D Nagase S Inorg Chem 2013 52 3585

[7] Kuwabara T Guo J D Nagase S Saito M Angew Chem Int Ed 2014 53 434

47

IL24

NEW METHODS FOR PEROXIDE SYNTHESIS

AO Terentev

ZIOCh Moscow Russia

In the last decades organic peroxides have received considerable attention from chemists and drug

design experts which is associated with a need in the search for drugs for the treatment of parasitic

diseases such as malaria and helminth infections Considerable progress has been made in the

design of effective peroxide antimalarial drugs Some synthetic peroxides exhibit activity equal to

or higher than that of artemisinin Peroxides having antitumor or growth-regulatory activity were

also documented In our work we developed new methods for synthesis of various types of

peroxides

It was found that some peroxides posesses pronounced antischistosomal properties and anticancer

activity This work is supported by the Grant of the Russian Foundation for Basic Research (Grant

14-03-00237) and by the Program for Basic Research of the Presidium of the Russian Academy of

Sciences

References

[1] Terentev A Borisov D Yaremenko I Chernyshev V Nikishin G JOrgChem 75 5065-

5071 2010

[2] Terentev A Yaremenko I Chernyshev V Dembitsky V Nikishin G JOrgChem 77

1833-1842 2012

[3] Ingram K Yaremenko IA Krylov I Hofer L Terentev A O Keiser J JMedChem 55

(20) 8700ndash8711 2012

[4] Terentev A O Yaremenko I A Vil V A Dembitsky V M Nikishin G I Synthesis

246-250 2013

[5] Terentev A O Yaremenko I A Vil V A Моisееv I K Konrsquokov S A Dembitsky V

M Levitsky D O Nikishin G I Org Biomol Chem 11 2613ndash2623 2013

[6] IA Yaremenko AO Terentrsquoev VA Vilrsquo RA Novikov VV Chernyshev VA Tafeenko

DO Levitsky F Fleury GI Nikishin Chemistry - A European Journal DOI

101002chem201402594

48

IL25

SYNERGISM BETWEEN THEORY AND EXPERIMENTS IN

ASYMMETRIC CATALYSIS TRANSITION STATE MODELING FOR

RATIONALIZATIONS AND CATALYST DESIGN

RB Sunoj

Department of Chemistry Indian Institute of Technology Bombay Powai Mumbai 400076

Computational quantum chemistry has been increasingly employed toward rationalizing the

stereochemical outcome of a diverse range of reactions1 The approach typically involves the

identification of kinetically significant transition states and intermediates In our laboratory ab

initio as well as DFT methods are employed to gain insights into carbon-carbon and carbon-

heteroatom bond-forming reactions of immediate practical significance2 The key objective is in

establishing the factors responsible for stereoselectivity in such reactions and to employ those

insights toward in silico design of novel catalysts for potential asymmetric applications3

A number of examples wherein the conventional transition state models required systematic

improvements toward accounting the observed product distribution and stereochemical outcome

will be presented In general the presentation would encompass a few contemporary themes in the

domain of organo- and organo-metallic catalysis Interesting interpretationsrationalizations of

experimental observations besides meaningful guidelines for rational improvements in asymmetric

catalysis would remain the key focus of the presentation The contents are designed to cater to a

broad and diverse group of audience hence the chemical insights would receive more emphasis

rather than intricate technical details

[1] (a) Cheong P H ndashY Legault C Y Um J M Celebi-Olcum N Houk K N Chem Rev

2011 111 5042 (b) Sunoj R B Wiley Interdisciplinary Reviews Comput Mol Sci 2011 1

920

[2] (a) Shinisha C B Sunoj R B J Am Chem Soc 2010 132 12135 (b) Sharma A K

Sunoj R B Angew Chem Int Ed 2010 49 9373 (c) Sharma A K Sunoj R B Chem

Commun 2011 47 5759 (d) Jindal G Sunoj R B Chem Eur J 2012 18 7045 (e) Jindal

G Sunoj R B Angew Chem Int Ed 2014 53 4432 (f) Anand M Sunoj R B Schaefer

H F J Am Chem Soc 2014 136 5535

[3] (a) Shinisha C B Sunoj R B Org Biomol Chem 2007 5 1287 (b) Shinisha C B Sunoj

R B Org Lett 2009 11 3242 (c) Jindal G Sunoj R B Org Bimol Chem 2014 12 2745

49

IL26

CATALYTIC ASYMMETRIC CROTYLATION METHOD DEVELOPMENT

AND APPLICATION IN TOTAL SYNTHESIS

AV Malkov PS Orsquohora CA Incerti-Pradillos MA Kabeshov

Loughborough University Loughborough LE11 3TU UK

Secondary metabolites 1-5 isolated from marine soft coral Pseudopterogorgia elisabethae exhibit a

wide range of useful biological properties which include anti-tubercular anti-inflammatory

antimicrobial and analgesic activities [1] The analgesic properties are superior to the existing

industry standards As a result partially purified gorgonian extracts are used in commercial skin

care products for topical applications [2]

H

OH

HO

Pseudopterosin A-Daglycone

H H

O

O

HO

H

OH

O

O

H

O

O

HO

HH

1 2 3 4

(ndash)-Elisapterosin B (ndash)-Colombiasin A(+)-Elisabethadione(+)-Erogorgiaene

5

Herein we present a novel general strategy for a scalable enantioselective total synthesis of

serrulatane diterpenes 1 and 2 Synthetically a major challenge associated with the synthesis of

these compounds is the control of the three stereocentres in the absence of directing functional

groups Our principal strategy is based on the asymmetric crotylation of cinnamyl-type aldehyde 10

with Z-crotyltrichlorosilane 9 to produce homoallylic alcohol 8 with a set of stereogenic centers that

will be used to control the stereochemistry of oxy-Cope rearrangement (8 rarr 7) and the subsequent

transformations towards the advanced intermediate 6 Development of novel efficient Lewis base

catalysts for the asymmetric crotylation and completion of the total synthesis of (ndash)-elisabethadione

and (ndash)-erogorgiaene will be discussed in detail

SiCl3O

OH

Cat

H

O

Anionic oxy-Cope

H

OH6

cationic cyclisation

Wittigolefination

12

7

810

Rn

Rn

RnRn

1

4

11

9

References

[1] A D Rodriguez C Ramirez J Nat Prod 2001 64 100-102

[2] A Kijjoa P Sawanwong Mar Drugs 2004 2 72-82

50

IL27

SYNTHESES OF METAL COMPLEXES WITH TRANS-CYCLOALKANE-

12-DIYL-[OSSO]-TYPE BIS(PHENOLATE) LIGAND AND ISOSPECIFIC

POLYMERIZATION OF ALPHA-OLEFINS

A Ishii

Department of Chemistry Graduate School of Science and Engineering Saitama University

Shimo-okubo Sakura-ku Saitama 338-8570 Japan

Efficiency and stereoselectivity of reactions catalyzed by metal complexes are often greatly affected

by auxiliary ligands of the catalysts We have recently developed tetradentate auxiliary ligands 1

featuring oxygen and sulfur coordination sites and fusion of trans-cycloalkane-12-diyl rings1ndash3

The

[OSSO]-bis(phenolate) ligand 1 (n = 3) was applied to the synthesis of zirconium complex 2 and we

found that a combination of 2 and an activator catalyzes the polymerization of 1-hexene with high

activity and high isospecificity1 in comparison with previously reported group 4 metal complexes

bearing [OSSO]-type ligands4 We have also synthesized Ti

5 Zr

6 Hf

7 V

8 Nb

8 Ta

8 and Al

9

complexes with 1 (n = 3) and investigated catalytic reactions with these complexes In this paper

we report the syntheses and structures of these metal complexes and their catalytic ability with

recent progress

S

SO

tBu

tBu

O

tBu

tBu

ZrCH2Ph

CH2Ph

1 2

S OH

tBu

tBu

OH

tBu

tBu

Sn

Bu 2(Ph3C)[B(C6F5)4] Bu Bu Bu Bu Bu

isotactic poly(1-hexene) ([mmmm] gt95)

activity =

2500 gbullmmolndash1bullhndash1

Mw = 59000 PDI = 17

References

1 Ishii A Toda T Nakata N Matsuo T J Am Chem Soc 2009 131 13566ndash13567

2 Ishii A Toda T Nakata N Matsuo T Phosphorus Sulfur Silicon 2011 186 1169ndash1174

3 Ishii A Asajima K Toda T Nakata N Organometallics 2011 30 2947ndash2956

4 Nakata N Toda T Ishii A Polym Chem 2011 2 1597ndash1610

5 Nakata N Toda T Matsuo T Ishii A Inorg Chem 2012 51 274ndash281

6 Toda T Nakata N Matsuo T Ishii A J Organomet Chem 2011 696 1258ndash1261

7 Nakata N Toda T Matsuo T Ishii A Macromolecules 2013 46 6758ndash6764 Nakata N

Saito Y Watanabe T Ishii A Top Catal 2014 57 918ndash922

8 Toda T Nakata N Matsuo M Ishii A ACS Catal 2013 3 1764minus1767

9 Nakata N Saito Y Ishii A Organometallics 2014 33 1840ndash1844

51

IL28

NEW APPROACH FOR THE SYNTHESIS OF COMPOUNDS CONTAINING

CF2 FRAGMENT

AD Dilman VV Levin AA Zemtsov MD Kosobokov

N D Zelinsky Institute of Organic Chemistry

Existing methods for the synthesis of compounds containing CF2 fragment either employ hazardous

reagents or require long synthetic sequence We propose a new approach towards difluorinated

compounds based on the coupling of three components mdash nucleophile difluorocarbene and

electrophile

As nucleophiles organometallic reagents can be employed The insertion of difluorocarbene into

carbon-zinc bond of organozinc reagents leads to new organozinc species which can be quenched

by halogen or proton1 or coupled with allylic electrophiles

2

The interaction of trimethylsilyl cyanide with difluorocarbene affords difluoro(trimethylsilyl)-

acetonitrile This reagent was used in reactions with aldehydes and imines furnishing fluorinated

alcohols and amines3 The addition products can be transformed into a variety of heterocyclic

molecules4

This work was supported by the Ministry of Science (project MD-475020133) and Russian

Foundation for Basic Research (projects 13-03-12074 14-03-00293 14-03-31253_mol_a 14-03-

31265_mol_a)

1 Levin V V Zemtsov A A Struchkova M I Dilman A D Org Lett 2013 15 917ndash919

2 Zemtsov A A Kondratyev N S Levin V V Struchkova M I Dilman A D J Org

Chem 2014 79 818ndash822

3 Kosobokov M D Dilman A D Levin V V Struchkova M I J Org Chem 2012 77

5850ndash5855

4 Kosobokov M D Struchkova M I Arkhipov D E Korlyukov A A Dilman A D

J Fluorine Chem 2013 154 73ndash79

52

IL29

TOWARDS REALISTIC FIRST-PRINCIPLES MODELLING OF

COMPLEXITY IN HETEROGENEOUS CATALYSIS

KM Neyman

ICREA and Universitat de Barcelona

Active components present in heterogeneous catalysts as nano-aggregates of thousands atoms

remain inaccessible for the first-principles (based on DFT) computations due to their size and

complexity However such species could be rather realistically represented by computationally

tractable smaller model nanoparticles (NPs) whose surface sites only marginally change the

reactivity with increasing particle size We illustrate this for decomposition of methane1 and

methanol2-4

on Pt and Pd catalysts as well as building of active sites on Ptceria catalysts56

We

show that using common slab models and thus neglecting the nanoscopic effects in these and

similar systems could lead to severe misrepresentation of the surface reactivity7

Methane decomposition on Pt NP is calculated to be more exothermic than on Pt(111) surface and

proceed via much lower activation barriers for the rate-limiting steps1 The reason for Pt activation

by nanostructuring is that CHx species are stabilized on NP edges converting the first two steps of

CH4 decomposition from endothermic on Pt(111) to exothermic on Pt79 The higher activity of edge

Pt atoms was assigned to their lower coordination and higher flexibility

The flexibility affects not only adsorption properties of sites with low-coordinated atoms but also

nearby terrace sites This effect is most pronounced for strongly bound adsorbates eg atomic C It

is a common by-product in decomposition reactions on Pd2 able to modify catalyst properties upon

exothermic migration subsurface34

The most spectacular effect of flexibility of Pd NPs is on the

subsurface migration barriers of surface C Near NPs edges these barriers essentially vanish

Presence of subsurface C makes Pd NPs more transparent for subsurface diffusion of adsorbed

hydrogen3 which in turn enables sustainable hydrogenation of olefins on Pd catalysts

Strong metal-support interactions can radically modify surface chemistry Due to catalysts

complexity the microscopic origin of such effects is usually unresolved However our study on

models of Pt-ceria catalysts succeeded to uncover atomic details of interactions in this system5

Calculations identified two types of oxidative Pt-ceria interactions electron transfer from a Pt

particle to the support and O transport from ceria to Pt The former is favorable on ceria supports

regardless their morphology But the O transfer requires the presence of Pt in close contact with

nanostructured ceria being inherently a nano-effect Both effects were detected by monitoring the

Ce3+

Ce4+

ratio using resonant photoelectron spectroscopy on Pt-CeO2 model catalysts

These case studies reveal very significant differences in the surface reactivity derived from

customary slab-model calculations and those employing dedicated NP models The latter expose a

variety of active sites whose structure and geometric flexibility notably better match those of the

sites present under experimental conditions Thus we advocate much broader usage of suitable NP

models in ldquocatalysis from first principlesrdquo 1 F Vintildees Y Lykhach T Staudt M P A Lorenz C Papp H-P Steinruumlck J Libuda K M Neyman A Goumlrling -

Chem Eur J 2010 16 6530

2 I V Yudanov A V Matveev K M Neyman N Roumlsch - J Am Chem Soc 2008 130 9342

3 K M Neyman S Schauermann - Angew Chemie Int Ed 2010 49 4743

4 H A Aleksandrov F Vintildees W Ludwig S Schauermann K M Neyman - Chem - Eur J 2013 19 1335

5 G N Vayssilov Y Lykhach A Migani T Staudt G P Petrova N Tsud T Skaacutela A Bruix F Illas K C Prince

V Matoliacuten K M Neyman J Libuda - Nature Mater 2011 10 310

6 A Bruix Y Lykhach I Matoliacutenovaacute A Neitzel K C Prince V Potin F Illas V Matoliacuten J Libuda K M

Neyman et al - Angew Chemie Int Ed 2014 53 doi 101002anie201402432

7 S M Kozlov K M Neyman - Top Catal 2013 56 86

53

IL30

С-С TRIPLE BOND ACTIVATION BY PLATINUM METALS UNDER

HOMO- AND HETEROGENEOUS CONDITIONS DESIGN OF NEW

CATALYTIC REACTIONS

SA Mitchenko

LM Litvinenko Institute of Physical Organic and Coal Chemistry National Academy of Sciences

of Ukraine Donetsk Ukraine

Petroleum and natural gas are the main sources of raw materials for modern bulk and fine chemical

industry Since the middle of the last century this changed the industry redirecting technology

previously based on acetylene towards olefinic stuff and synthesis gas Nevertheless series of large-

scale (for example manufacture of vinyl ethers pyrrolidone and N-methylpyrrolidone butanediol

etc) and fine (drugs and fragrances crop protecting agents etc) chemical production based on

acetylene hydrocarbons possesses definite advantages and is still developing Besides acetylene

hydrocarbons are inevitably formed as by-products in oil processing yielding olefins and taking

into account the modern industrial scales and prices of starting materials these by-products should

be efficiently utilized On the other hand coal and natural gas supply as against of petroleum allow

us to regard them as practically inexhaustible source of acetylene Increasing interest to the catalytic

chemistry of acetylene (see for example [1 2]) can be motivated in particular by these

considerations

Results of development of new catalytic transformations of acetylene under homo- and

heterogeneous conditions will be presented and discussed

References

1 Alonso F Beletskaya IP Yus M Chem Rev 2004 104 3079

2 Ananikov V P Beletskaya I P Organometallics 2012 31 1595

54

IL31

SYNERGISTIC EFFECTS IN DESIGNING COMBINED CATALYTIC

SYSTEMS (COMBICATrsquoS) FOR ABATEMENT OF

NITROGEN OXIDES (NOX)

AYu Stakheev

Zelinsky Institiute of Organic Chemistry Catalysis division Moscow Russia

Anthropogenic emission on nitrogen oxides (NOx = NO NO2 N2O) becomes an important issue

since the amount of anthropogenic NOx nowadays exceeds biogenic emission (~110 Mt vs 80

Mtannual) and their impact on environment is significant The most effective method for

abatement of nitrogen oxides is their selective catalytic reduction (SCR) by urea or NH3

2NO + 2NH3 + 12O2 = 2N2 + 3 H2O

However activity of the traditional NH3-SCR catalysts at the temperatures below 250oC is not

sufficient due to the stringent restrictions imposed by environmental legislations on NOx emission

from mobile sources The effective solution can be provided by Cu-containing zeolite catalyst

however high cost often limits their practical application Our recent study revealed alternative

approach and indicated that promising NH3-DeNOx activity at Treact lt 250degC CAN BE ATTAINED OVER

combined catalysts (CombiCat) comprising zeolite component (possessing high activity in SCR)

and a redox component (having high activity in NO oxidation) For such compositions we found a

pronounced synergistic effect and the catalytic activity of the COMBICATrsquoS significantly exceeds

activity of the individual components A number of compositions have been tested for searching

synergistic effects and the most remarkable results have been observed for [CuAl2O3 +FeBETA]

[MnAl2O3 + FeBETA [CeZr +FeBETA] [MnCeZr + FeBETA] MnFeBETA Interestingly that

the studied composition exhibits favorable performance in selective oxidation of NH3

2NH3 + 32 O2 = N2 + 3H2O

Therefore CombiCatrsquos are capable to accomplish two functions SCR catalyst and removal of

residual NH3 In addition to that for the compositions comprising CeO2-ZrO2 component a

promising soot oxidation activity has been observed

Detailed study of a possible origin of the observed synergistic effects suggests that the improvement

of NH3-DeNOx activity can be attributed to a ldquodual functionrdquo reaction mechanism comprising two

main stages

(1) NO + O2 harr NO2 over redox component

(2) NO + NO2 + 2NH3 rarr N2 + 3H2O over zeolite component

However further research is required for revealing overall reaction network and understanding

reaction mechanism responsible for observed synergy

55

IL32

NOVEL COLCHICINOIDS AS POTENTIAL ANTITUMOR AGENTS

A Yu Fedorov

Department of Organic Chemistry Nizhny Novgorod State University Gagarina av 23 Nizhny

Novgorod 603950 Russian Federation

A range of indole - and furane-containing allocolchicinoids was synthesized

Several from synthesized compounds manifested high in vitro and in vivo antitumor activity

Acknowledgment

We thank the Russian Foundation for Basic Research (projects 14-03-91342 and 12-03-00214-a)

The Ministry of Education and Science of The Russian Federation (project 46192014K) The

research is partly supported by the grant 02В49210003 of The Ministry of Education and

Science of the Russian Federation to Lobachevsky State University of Nizhni Novgorod

56

IL33

ENANTIOSELECTIVE CATALYSIS BY CHIRAL BROslashNSTED ACIDS AND

CHIRAL BRШNSTED BASES

M Terada

Tohoku Univsersity Department of Chemistry Sendai Japan

Chiral phosphoric acids 1 have become one of the most versatile types of chiral Broslashnsted acid

catalysts identified to date and have been applied to a broad range of enantioselective

transformations12)

In my continuing efforts to broaden the scope of enantioselective catalysis by 1

activation of oxygenated functional groups other than imines and related functional groups is our

recent research interest To expand the scope of chiral Broslashnsted acid catalysis recently a novel

chiral bis-phosphoric acid 2 was developed as a highly active and efficient enantioselective

catalyst3)

On the other hand intense interest has been devoted to the development of chiral

uncharged organosuperbase catalysts during the past decade In an effort to develop efficient chiral

organobase catalysts we designed and synthesized unique axially chiral Broslashnsted base 34)

3

functioned as the efficient enantioselective catalysts for the activation of pro-nucleophile having a

relatively acidic proton such as 13-dicarbonyl compounds To expand the scope of chiral Broslashnsted

Base catalysis development of much stronger organosuperbase is highly demanded We hence

designed a pseudo C2-symmetric bis(guanidino)iminophosphorane 4 as a novel family of chiral

organosuperbases5)

In my presentation I briefly introduce these chiral Broslashnsted acid catalysts (1

and 2) and base catalysts (3 and 4) In particular I would like to present a novel chiral Broslashnsted

base catalyst 4 in details

References

1) (a) Terada M Synthesis 2010 1929-1982 (b) Terada M Chem Commun 2008 4097-4112

2) Uraguchi D Terada M J Am Chem Soc 2004 126 5356-5357

3) Momiyama N Konno T Furiya T Iwamoto T Terada M J Am Chem Soc 2011 133

19294-19297

4) Terada M Ube H Yaguchi Y J Am Chem Soc 2006 128 1454-1455

5) Takeda T Terada M Y J Am Chem Soc 2013 135 15306-15309

57

IL34

IONIC LIQUIDS WATER AND LIQUID OR SUPERCRITICAL CO2 AS

PERSPECTIVE MEDIA FOR ASYMMETRIC ORGANOCATALYSIS

SG Zlotin

ND Zelinsky Institute of Organic Chemistry Russian Academy of Sciences

Over the last decade amazing results have been associated with the extensive application of

asymmetric organocatalysts in organic synthesis In the presence of small metal-free chiral organic

molecules (α-amino acid or cinchona alkaloid derivatives BINOL phosphoric acids and other

chiral compounds) available prochiral reagents can be easily converted into chiral products of high

molecular complexity in high yields and with excellent enantioselectivities Unlike organometal

catalysts organocatalysts do not contaminate products with toxic heavy metals and this is important

in terms of medicinal chemistry However in some cases they may be responsible for hardly

separable and potentially dangerous organic impurities

To facilitate product purification and recovery of precious chiral catalysts immobilized forms of

organocatalysts tagged to polymers or ionic groups have been designed and organocatalytic

reactions have been carried out in so called ldquoneotericrdquo green solvents particularly in ionic liquids

(IL) water and liquid or supercritical (sc) carbon dioxide In these systems a catalyst and a product

are located in different phases during the catalytic process andor the working-up step

We developed highly efficient enantioselective cross-aldol reactions between various carbonyl

compounds in the presence of proline or prolinamide-derived organocatalysts in the IL andor

aqueous environment An original method for adapting -amino acid-sourced IL-supported chiral

organocatalysts to the aqueous medium via an incorporation of long-chain alkyl groups and

hydrophobic anions into their molecules and by performing asymmetric reactions in reagentswater

two-phase systems was elaborated Corresponding aldol products were obtained in high yields and

with extremely high anti -diastereo- (dr up to 98 2) and enantioselectivities (ee up to 99) under

proposed conditions After product isolation the remaining catalyst-water heterogeneous system

could be reused up to 15 times without a decrease of product yield and selectivity of the reaction1

Carbon acids in particular malonates malononitrile and anthranone appeared to react

enantioselectively with nitroalkenes in the presence of tertiary aminethiourea-derived bifunctional

organocatalyst in liquid CO2 as a green substitute of toxic organic solvents to afford the respective

Michael adducts in moderate to high yields and with enantioselectivities of up to 92 ee2 The first

ldquogreenrdquo asymmetric organocatalytic reaction in sc-CO2 namely a bifunctional squaramide-

catalyzed addition of diphenylphosphite to α-nitroalkenes to afford β-nitrophosphonates in high

yields and with ee-values of up to 94 was elaborated3 In this way the most active (R)-enantiomer

of the therapeutically useful GABAB receptor agonist baclofen a key precursor of the chiral

anticonvulsant pregabalin and both enantiomers of pharmacologically important β-amino

phosphonic acid derivatives were synthesized A significant potential of the supercritical extraction

for product isolation and catalyst recovery which completely eliminates the use of organic solvents

during the working-up procedure was demonstrated

The work was financially supported by the Russian Foundation of Basic Research (projects 12-03-

00420 14-03-31321 and 14-03-92701)

1 DE Siyutkin AS Kucherenko SG Zlotin In ldquoComprehensive Enantioselective

Organocatalysis Catalysts Reactions and Applicationsrdquo ed by PI Dalco Wiley-VCH 2013

v 2 p 617-650

2 AG Nigmatov IV Kuchurov DE Siyutkin SG Zlotin Tetrahedron Lett 2012 53 3502

3 IV Kuchurov AG Nigmatov EV Kryuchkova AA Kostenko AS Kucherenko SG

Zlotin Green Chem 2014 16 1521

58

IL35

MAKING OLEFIN METATHESIS WORK - RECENT RESULTS IN

RUTHENIUM CATALYSTS DESIGN

KL Grela

Biological and Chemical Research Centre Faculty of Chemistry University of Warsaw

Ruthenium-catalyzed olefin metathesis reactions represent an attractive and powerful

transformation for the formation of new carbon-carbon double bonds [1] This area is now quite

familiar to most chemists as numerous catalysts are available that enable a plethora of olefin

metathesis reactions [1] However formation of substituted and crowded double bonds decreasing

the amount of metal using metathesis in green context etc still remain a challenge making

industrial applications of this methodology difficult [2] These limitations can be solved by

designing new more active and stable catalysts and catalysts that can be easier removed recycled

[3]

During the lecture a number of representative examples will be presented

Artwork copy Katarzyna Felchnerowska wwwfbcomeffefineart

References

[1] Olefin Metathesis Theory and Practice Grela K (Ed) John Wiley amp Sons 2014

[2] Thayer A Chemical amp Engineering News 2007 85 (07) 37

[3] Clavier H Grela K Kirschning A Mauduit M Nolan S P Angew Chem Int Ed 2007

46 6786-6801

59

60

Oral Communications

61

62

OC1

THE FIRST CYCLOPENTADIENYL NICKEL COMPLEXES BEARING A

SILYL GROUP OR HYDROGEN SUBSTITUTED PHOSPHINE

CHELATING SIDECHAIN

I Werner H Butenschoen

Institute of Organic Chemistry Leibniz Universitaet Hannover Hannover Germany

The only known secondary phosphine pendant cyclopentadienyl complexes are those of zirconium

and hafnium reported by Ishiyama et al in 2002[1]

Since these complexes contain a reactive

phosphorus-hydrogen bond they were converted into the corresponding phosphide-substituted

cyclopentadienyl chelate complexes[2]

Both systems were successfully applied in catalytic ethylene

and styrene polymerization reactions as well as in ethylenestyrene copolymerization reactions[3]

To our knowledge no analogous complexes of late transition metals containing a phosphorus-

hydrogen or a phosphorus-silyl bond have so far been reported We report on the synthesis of the

first cyclopentadienyl nickel complexes 1-4 and 5 7 bearing a silyl group and hydrogen substituted

phosphine chelating sidechain respectively

Treatment of complex 5 with SIMes induced the decomplexation of the secondary phosphane

substituted tether delivering exclusively nickel carbene complex 6

Recrystallization of complex 7 from hexaneethyl acetate (11) at 30 degC afforded crystals suitable

for an X-ray crystal structure analysis

References

[1] T Ishiyama H Nakazawa K Miyoshi J Organomet Chem 2002 648 231

[2] T Ishiyama T Mizuta K Miyoshi H Nakazawa Organometallics 2003 22 1096

[3] T Ishiyama K Miyoshi H Nakazawa J Mol Cat A-Chem 2004 221 41

63

OC2

EXPANDED RING N-HETEROCYCLIC CARBENE TRANSITION METAL

COMPLEXES SYNTHESIS STRUCTURE APPLICATIONS IN

CATALYSIS

MS Nechaev1 AF Asachenko

2 PB Dzhevakov

2 OS Morozov

2 GV Proskurin

1 PS

Gribanov1

1 - Moscow State University Department of Chemistry Moscow Russia

2 - A V Topchiev Institute of Petrochemical Synthesis RAS Moscow Russia

N-heterocyclic carbenes (NHCs) became widely used as organocatalysts and as ligands in transition

metal catalysis Most of NHC-metal complexes known to date are derived from five-membered ring

imidazol-2-ylidene and imidazolin-2-ylidene type carbenes In recent years our group develops

chemistry of 6- 7- and 8-membered ring carbenes Expanded ring carbenes (er-NHCs) exhibit

superior stereoelectronic properties in comparison with five-membered ring counterparts

Expansion of the ring leads to significant increase in donor strength and sterical hindrance

In this contribution we report our recent results on theoretical calculations of electronic structure

and ligand properties of er-NHCs efficient methods of synthesis of precursors and generation of

free carbenes synthesis of late transition metal (Cu Ag Au Pd) complexes It was found that er-

NHC complexes of palladium are highly active in Suzuki-Miyaura coupling in water and

dimerization of terminal alkynes with formation of E-enynes Cationic gold complexes are active

catalysts of addition of nucleophiles to carbon-carbon triple bonds

64

OC3

PALLADIUM-CATALYZED CndashH ALKENYLATION OF ARENES USING

SULFUR-CONTAINING DIRECTING GROUPS A COMPARATIVE STUDY

KV Luzyanin AN Marjanov VP Ananikov

Laboratory of Cluster Catalysis Saint Petersburg State University Universitetsky pr 26 Stary

Petergof 198504 Russia

Direct alkenylation of organic substrates via directing-group assisted functionalization of the CH

bond has emerged as a valuable tool for creation of new sp2-sp

2 bonds In the contrast to the

MirozokindashHeck reaction that starts from the aryl halides this procedure works with inactivated

arenes and is favorable from both economical and environmental points of view Several types of

directing groups have been evaluated in the direct alkenylation up to date eg ketones and

carboxylates amides pyridine sulfoxides and ethers and thioethers Among them functionalization

of sulfur-containing compounds (Scheme 1) ie pyridine thioesters and sulfoxides as well as

structurally related benzylic thioethers (in those sulfur moiety plays a role of a directing group)

attracts rapidly growing attention On the one hand functionalization of such compounds leads to

interesting derivatives containing both alkene and sulfur functions while on the other hand sulfur-

based directing groups in these species can be easily removed after reaction from the resulting

products without compromising other functionalities1ndash3

Scheme 1 Direct alkenylation of arenes using sulfur-containing directing groups

In the current report we summarize data accumulated up to date regarding direct CH-alkenylation

of sulfur-containing organic compounds A particular emphasis is given to the evaluation of the

assistance provided by different sulfur-containing directing groups in comparison to other common

directing moieties known to be employed for this purpose

Acknowledgements This work has been partially supported by the Saint Petersburg State

University (research grant from Laboratory of Cluster Catalysis) and the Russian Fund for Basic

Research (grant 14-03-01005)

References 1 Garciacutea-Rubia A Fernaacutendez-Ibaacutenez M A Goacutemez Arrayaacutes R Carretero J C Chem Eur J

2011 17 3567ndash3570

2 Yu M Xie Y Xie C Zhang Y Org Lett 2012 14 2164ndash2167

3 Zhang X-S Zhu Q-L Zhang Y-F Li Y-B Shi Z-J Chem Eur J 2013 19 11898ndash

11903

65

OC4

IN PURSUIT OF A NOVEL IMIDATE-BASED SALEN-TYPE LIGAND

CLASS

J Van Der Eycken1 P Janssens

1 T Noel

2

1 - Ghent University Department of Organic Chemistry

2 - Eindhoven University of Technology Department of Chemistry and Chemical Engineering

Micro Flow Chemistry amp Process Technology

An increasing ecological awareness and global competitiveness have challenged the chemical

industry towards a higher level of sustainability through innovation and technology In research the

majority of topics on sustainable process development deals with catalysis[1]

Furthermore in

organic synthesis transition metal catalysis already plays a vital role in the synthesis of biologically

active compounds[2]

N N

OH HO

N N

H H H HO O

OH HO

L1 L2

Bisimidate ligand L2 shows striking similarities with Salen ligands (L1) We reasoned that this

could open new opportunities for our already well-established imidate ligand family [3-5]

Nevertheless the applicability of this ligand in the MnV-catalyzed asymmetric epoxidation reaction

turned out to be more complicated than expected

In this communication the search towards an effective novel imidate-based Salen-type ligand class

will be discussed from a ligand design point of view

References

[1] Dichiarante V Ravelli D Albini A Green Chem Lett Rev 2010 3 105

[2] a) Noyori R Angew Chem Int Ed 2002 41 2008 b) Busacca CA Fandrick DR Song

JJ Senanayake CH Adv Synth Catal 2011 353 1825

[3] a) Noeumll T Bert K Van der Eycken E Van der Eycken J Eur J Org Chem 2010 21

4056 b) Bert K Noeumll T Van der Eycken J Org Biomol Chem 2012 10 8539 c) Noeumll T

Bert K Janssens P and Van der Eycken J (2012) ldquoChiral Imidate Ligands Synthesis and

Applications in Asymmetric Catalysisrdquo in Innovative Catalysis in Organic Synthesis

Oxidation Hydrogenation and C-X Bond Forming Reactions (ed P G Andersson) Wiley-

VCH Verlag GmbH amp Co KGaA Weinheim Germany doi 1010029783527646586ch14

66

OC5

NITROALKANES IN PPA AS NEW REAGENTS FOR DIRECT METAL-

FREE AMINATION OF ARENES

AV Aksenov1 NA Aksenov

1 IV Aksenova

1 M Rubin

2 DA Aksenov

1

1 - Department of Chemistry North Caucasus Federal University Stavropol Russian Federation

2 - Department of Chemistry University of KansasLawrence USA

Aromatic amines represent an important class of organic compounds Many of them demonstrate

important biological activities Various multi-step methods for preparation of these compounds

have been developed including electrophilic nitrationreduction sequence Schmidt and Beckmann

rearrangements etc The most appealing methods however are those that allow for direct

introduction of an amino-group to a non-substituted arene over a single step

Direct electrophilic acetamidation of arenes 2 with primary nitroalkanes 1 in polyphosphoric acid

(PPA) recently developed in our laboratories can be viewed as an example of such an approach

R

N+

O

O

P P A

R

N+

O

O P

O

O H

O R

2

R3

R1

R4

R2

N

R

O

PO

O H

O

R3

R4

R1

R2

NH

R

OR3

R1

R4

6 3 -9 2

2

1

3 R=Me Pr Ph Bn R

1 R

2 R

3 R

4=H Me OH MeO CHO

Benzene and arenes with electron-donating substituents can be engaged in this reaction Electron

deficient arenes are inert The process is highly selective the electrophilic attack is always directed

to para-position with respect to a substituent already present in the ring

Anthracene 4 and indole 5 were successfully involved into the acetamidation reaction In reaction of

dibenzo-18-crown-6 ether monoacetamide was formed along with quite a large amount of bis-

acetamination isomeric products

The reaction involving secondary nitroalkanes is also interesting Since the nitroso compound 4

resulting from electrophilic attack to the aromatic ring is not able to isomerize oxime it attacks a

second molecule of arene After rearrangement this leads to the formation of diarylamines 5

N+ O

O P O2H

- H +N

O H

O P O2H

R1

R2

P P A

O

R1

R2

NO

R1

R2

- H2O R

1

R2

N

O HR

1

R2

R1

R2

R1

R2

N

O H

R1

R2

R1

R2

NH

+-P P A

+

4

5 5 5 -6 1 R

1 R

2 =H Me MeO CHO

A novel protocol for direct and regioselective metal-free acetamination and amination of arenes in

reactions with primary and secondary nitroalkanes in polyphosphoric acid media was developed A

new preparative approach to 5-aminoindoles and diarylamines employing this reaction was

demonstrated

This work was carried out with financial support from the Russian Foundation Basic Research

(grants 13-03-00304 a and 14-03-31288 mol_a)

67

OC6

UROTROPINE ISOMER (14610-TETRAAZAADAMANTANE)

MOLECULAR SIMPLICITY AND MOLECULAR COMPLEXITY OF

HETEROADAMANTANE CAGE

AYu Sukhorukov AN Semakin IS Golovanov SL Ioffe VA Tartakovsky

ND Zelinsky Institute of Organic Chemistry Moscow Russia

For more than 100 years heteroadamantanes have been objects of rapt attention for fundamental

and applied chemistry These cage polycyclic systems represent interest not only due to their unique

properties but also as convenient models for the study of basic problems dealing with structure and

reactivity of organic compounds Among many heteroadamantanes 1357-tetraazaadamantane

(urotropine) which was first obtained by A Butlerow in 1859 plays probably the most important

role from an applied point of view Urotropine is widely used in medicine polymer production

food industry as well as organic synthesis coordination chemistry and MOFs design This simplest

Td-symmetrical 1357-tetraazaadamantane is the only known representative of the class of

tetraazaadamantanes In this context the possibility of existence of other tetraazaadamantanes

isomeric to urotropine represents considerable fundamental interest

The present report deals with the first synthesis of 14610-tetraazaadamantane (ldquoisourotropinerdquo)

the C3v-symmetrical structural isomer of urotropine and a series of its derivatives (see Figure) X-

Ray and quantum-chemical studies demonstrate remarkable distinctions in structures of urotropine

and ldquoisourotropinerdquo cages probably arising from different types of lp(Neq) C N interactions in

these heterocage systems Since substitution at bridge and bridgehead nitrogen atoms can be easily

installed 14610-tetraazaadamantane can be considered as a new rigid multivalent (3+1) scaffold

for the design of complex functional molecules and materials

Acknowledgement

The financial support from RFBR (grant 14-03-00933a) and Russian Presidentrsquos Council for Grants

(grant MK-391820133) is greatly acknowledged

68

OC7

PALLADIUM-CATALYZED CROSS-COUPLING REACTION OF

ALCOHOL WITH ARYL CHLORIDE THROUGH C-C BOND ACTIVATION

C-H Jun H-S Park D-S Kim

Yonsei University Department of Chemistry Seoul South Korea

The C-C bond activation is one of challenging subjects in organometallic chemistry1 Especially

catalytic version of C-C bond activation has been recently achieved by chelation assisted transition

metal catalyst consisted of Rh(I) and 2-amino-3-picoline2 During the course of our studies on

these types of C-C bond activation we found decarbonylative esterification of aliphatic alcohol

with aryl chloride by palladium metal as shown below For example when the reaction of

chlorobenzene and 1-naphtylethanol was carried out at 150oC under PdC and NaF base a mixture

of three products 1-naphtylethyl benzoate ester benzene and 1-methylnaphthalene was obtained

in reasonable yields

The reaction mechanism is proposed as follows The reaction proceeds through several consecutive

reactions Initially primary alcohol is oxidized by aryl chloride to aldehyde with formation of aryl-

H under palladium catalyst Aldehyde is decarbonylated by Pd to generate alkane and (CO)Pd The

intermediate (CO)Pd is oxidatively added to aryl chloride to form acyl-PdCl complex which reacts

with alcohol to give ester compounds In this reaction reactivity of substrate should be well

balanced The reactivity of chloroarene is suited for this purpose since other aryl halide such as

bromobenzene and iodobenzene did not show any reactivity in this reaction This result is quite

interesting since aryl chloride is least reactive for common C-C bond coupling reaction while aryl

iodide is very reactive The reaction works well with aryl chloride One of merits in this protocol is

that carbonylation proceeds without using toxic CO gas and CO source is non-toxic alcohol More

detailed mechanistic studies using 13

C-enriched or deuterated alcohol will be discussed

References

1 Jun C -H Chem Soc Rev 2004 33 610-618

2 Park Y J Park J -W Jun C -H Acc Chem Res 2008 41 222-234

69

OC8

RADICAL-CATIONS OF ACETYLENE COMPOUNDS IN CARBON-

CARBON BOND FORMING REACTIONS

AV Vasilyev

Saint Petersburg State Forest Technical University Institutsky per 5 Saint Petersburg 194021

Russia Saint Petersburg State University Institute of Chemistry

Radical-cations of acetylene compounds A generated under oxidation of alkynes I in systems

PbO2-strong acid (CF3CO2H HF HSO3F) are key reaction intermediates in various new carbon-

carbon bond forming processes [1-6]

Depending on structure the species A lead to formation of a variety of products II-VII When

substituents X are moderate electron acceptors CO2R COAr COR PO(OEt)2 trans-ethenes II are

stereoselectively formed In case of stronger acceptors furan derivatives III (X = COCF3

СОCO2Et) or diketones IV (X = CF3) are formed

In different acidic systems radical-cations of diarylacetylenes (X = Ar) give unsaturated diketones

V (in CF3CO2H) butadiene difluiorides VI (in HF) or dichlorides VII (in HSO3F followed by

quenching in HClaquaconc) The last ones are electro-cyclically converted into naphthalenes VIII

C

C C

C

Ar Ar

FF

Ar Ar

C C

Ar

C C

Ar

Cl Cl

Ar Ar

CC

C

O O

C

Ar Ar

ArAr

Cl

Ar

Ar

Ar

R

H+ = CF3CO2H

H+ = HF

1 H+=HSO3F 2 HCl

VI

VIII

X = COCF3

COCO2EtC

OX

C C

C

OC

Ar

Ar Y

C

OX

C C

C

OX

Ar

ArX = CO2Alk

COAr COMe

PO(OEt)2

C C X

C CAr

I

A

III

II-e

Ar

X

PbO2H+

CF3F3C

C C

C

O O

C ArArHH

X = CF3

Y = CF3 CO2Et

X = Ar

IVV

X = Ar

X = Ar

VII

[1] Vasilyev AV Rudenko AP Russ J Org Chem (in Engl) 1997 V33 P 1555-1584

[2] Shchukin AO Vasilyev AV Fukin GK Rudenko AP Russ J Org Chem (in Engl)

2007 V43 P1446-1450

[3] Vasilyev AV Aristov SA Fukin GK Kozhanov KA Bubnov MP Cherkasov VK Russ

J Org Chem (in Engl) 2008 V44 P 791-802

[4] Vasilyev AV Shchukin AO Walspurger S Sommer J Eur J Org Chem 2008 4632

[5] Vasilyev AV Rudenko AP Russ J Org Chem (in Engl) 2010 V46 P1282-1289

[6] Alkhafaji HMH Vasilyev AV Ryabukhin DS Rudenko AP Muzalevskiy VM

Nenajdenko VG Russ J Org Chem (in Engl) 2013 V49 P 621-623

70

OC9

ACTIVATION OF Ru-BASED OLEFIN METATHESIS CATALYSTS

A Poater1 L Cavallo

2

1 - Institut de Quimica Computacional i Catаlisi and Departament de Quimica Universitat de

Girona Campus de Montilivi E-17071 Girona Catalonia Spain

2 - Kaust Catalysis Center Physical Sciences and Engineering Division King Abdullah University

of Science and Technology Thuwal 23955-6900 Saudi Arabia

In recent years olefin metathesis catalyzed by N-heterocyclic carbene ruthenium complexes has

attracted remarkable attention as a versatile tool to form new C=C bonds[1] The last developed

(pre)catalysts show excellent performances and this achievement has been possible because of

continuous experimental and computational efforts to understand the laws controlling the behavior

of these systems This perspective talk rapidly traces the ideas and discoveries that computational

chemistry contributed to the development of these catalysts with particular emphasis on catalysts

presenting a N-heterocyclic carbene ligand Specifically one of the most important challenges in

ruthenium-catalyzed olefin metathesis is to increase the stability of the catalysts under reaction

conditions and this hopefully without loss of activity Special interest has been addressed to study

the activation of the second-generation Grubbs catalysts which has clarifier either a dissociative or

an interchange mechanism is feasible[2]

Although in the solid state most ruthenium-based olefin metathesis catalysts are stable to oxygen

and moisture in solution decomposition usually occurs readily Understanding the decomposition

routes of catalysts is extremely important as any insight gained in this area can guide catalyst design

efforts to participate then in the synthesis of drugs[34] Furthermore new challenging projects

plan to modify the structure of the NHC ligands or replace this ligand by alkylidene ligands and

even the substitution of the metal is a goal moving to more environmentally friendly metals

[1] G C Vougioukalakis R H Grubbs Chem Rev 110 1746 (2010)

[2] C A Urbina-Blanco A Poater T Lebl S Manzini A M Z Slawin L Cavallo S P Nolan

J Am Chem Soc 135 7073 (2013)

[3] S Manzini C A Urbina-Blanco A Poater A M Z Slawin L Cavallo S P Nolan Angew

Chem Int Ed 51 1042 (2012)

[4] S Manzini A Poater D J Nelson L Cavallo S P Nolan Chem Sci 5 180 (2014)

71

OC10

CHEMICAL REACTIVITY IN PROTEINS AND WATER QMMM MD

INSIGHTS INTO EFFECTS OF LOCAL STRUCTURAL ENVIRONMENTS

ON BOND CLEAVAGE

Y Zhao BJ Wang RB Wu ZX Cao

Department of Chemistry Xiamen University Xiamen 361005 China

Water and proteins play a quite important role in chemical and biological processes In past few

years we carried out a systematic investigation on the effect of local structural environments on

reactivity towards hydrolysis C-N C-O and C-H bond cleavages in proteins and water Using

Born-Oppenheimer ab initio QMMM MD simulations a state-of-the-art approach to simulating

enzymes we have investigated the structural features of zinc enzymes nucleoside hydrolase and

deaminase and plausible enzymatic mechanisms The molecular complexity of active domain in

enzyme and roles of conserved residues and protein environments in enzymatic catalysis have been

explored In particular the different coordination modes and fast ligand exchanges of zinc

coordination has been suggested to be one key catalytic feature of the zinc ion and the chelation

mode of hydroxamate with the zinc ion in HDACs is modulated by water access to the linker

binding channel This new insight into the interplay between the linker binding and the zinc

chelation emphasizes its importance for the development of new class-IIa-specific HDAC

inhibitors Our calculations indicate that the reliable theoretical treatment on the water-mediated

proton transfer and most hydrolysis reactions of carbonyl compounds such as aldehydes ketones

esters amides the carboxylic acids and their derivatives requires use of the large basis set and

suitable cluster-continuum model The effects of solvent and structural modification on hydration

and hydrolysis of carbonyl compounds have been discussed

Acknowledgements This work was supported by the National Science Foundation of China

(21133007 and 21373164) and the Ministry of Science and Technology (2011CB808504)

References

1 N Chen H Ge J Xu Z Cao and R Wu Biochim Biophys Acta 2013 1834 1117

2 R Wu W Gong T Liu Y Zhang and Z Cao J Phys Chem B 2012 116 1984

3 B Wang and Z Cao Chem Eur J 2011 17 11929

4 B Wang and Z Cao Angew Chem Int Ed 2011 50 3266

5 R Wu Z Lu Z Cao and Y Zhang J Am Chem Soc 2011 133 6110

6 Y Zhao N Chen R Wu and Z Cao 2013 submitted

72

OC11

MECHANISM OF INTRAMOLECULAR HECK REACTION BY DENSITY

FUNCTIONAL THEORY

A Ayyappan D Yogeswara Rao

Indian Institute of Technology Kharagpur Department of Chemistry West Bengal 721392 India

Heck Reaction the palladium-catalyzed C-C coupling between aryl halides or vinyl halides and

activated alkenes in the presence of a base is widely used in syntheric chemistry Intramolecular

version of Heck reaction is a route to the generation carbocycles that are scaffolds of many

important natural products and biologically active molecules Although the mechanism of

intermoelcular Heck reactions is well established the intramelecular variant is not analyzed in detail

for its mechanistic features Using Density Functional Theory computations we have explored the

the catalytic cycle of intramolecular Heck reaction that involves oxidative addition migratory

insertion (cyclization) and β-hydride elimination (See Figure) Two pathways were analyzed which

differ in their initial coordination face (Re or Si) of the terminal alkene with the metal centre The

choice of pathway is not evident from free energy profile because one of the pathways have higher

barrier for oxidative addition the other requires high activation energy for β-hydride elimination

Detailed analysis of the mechanism will be presented In addition our attempts to analyze such

complex reaction mechanisms by kinetic simulations will be discussed

Figure Catalytic cycle for the intramolecular Heck reaction

73

OC12

CYCLODIMERIZATIONS OF DONOR-ACCEPTOR CYCLOPROPANES

SHORTCUT APPROACH TO COMPLEX RING SYSTEMS

EM Budynina OA Ivanova AO Chagarovskiy IV Trushkov

Moscow State University Department of Chemistry Moscow Russia

Cyclodimerization is among the most challenging and fascinating reactions providing significant

increase in structural complexity within one operation step in highly stereoselective manner and

occurring both in vivo and in vitro In organic synthesis among typical substrates that undergo

cyclodimerizations donor-acceptor (DA) cyclopropanes1 in which small ring is vicinally activated

with donor and acceptor groups occupy a special place Currently at least dozen types of Lewis

acid-triggered cyclodimerization of such DA cyclopropanes as 2-(het)aryl-cyclopropane-11-

diesters are known which open rapid approaches to diverse ring compounds including complex

polycyclic and bridged molecular systems2

Recently on basis of (3+3)-cyclodimerizations of 2-arylcyclopropane-11-diesters we developed

straightforward and efficient approaches to 14-diarylcyclohexanes 1-aryltetralins or 910-

dihydroanthracenes2a

(3+2)-Cyclodimerizations of similar cyclopropanes provide an easy access to

diarylcyclopentanes2bc

and arylindanes2d

Cyclodimerizations of 3- and 4-indolyl-derived DA

cyclopropanes allows for the construction of complex tetra- and heptacyclic cores of bisindoles2e

1 a) Reissig H-U Zimmer R Chem Rev 2003 103 1151 b) De Simone F Waser J

Synthesis 2009 3353 c) Melrsquonikov MYa Budynina EM Ivanova OA Trushkov IV

Mendeleev Commun 2011 21 293 d) Schneider TS Kaschel J Werz DB Ang Chem Int

Ed 2014 53 101002anie201309886

2 a) Ivanova OA Budynina EM Chagarovskiy AO Trushkov IV Melnikov MYa J

Org Chem 2011 76 8852 b) Chagarovskiy AO Ivanova OA Budynina EM Trushkov

IV Melnikov MYa Tetrahedron Lett 2011 52 4421 c) Novikov RA Korolev VA

Timofeev VP Tomilov YuV Tetrahedron Lett 2011 39 4996 d) Ivanova OA Budynina

EM Skvortsov DA Limoge M Bakin AV Chagarovskiy AO Trushkov IV

Melnikov MYa Chem Commun 2013 49 11482 e) Ivanova OA Budynina EM

Chagarovskiy AO Rakhmankulov ER Trushkov IV Semeykin AV Shimanovskii NL

Melnikov MYa Chem Eur J 2011 17 11738 f) Novikov RA Tarasova AV Korolev

VA Timofeev VP Tomilov YuV Ang Chem Int Ed 2014 53 3187 g) Novikov RA

Tomilov YuV Helv Chim Acta 2013 96 2068

74

OC13

USING RING STRAIN RELEASE FOR ALLEVIATION OF

TRANSANNULAR STRAIN SMALL RING-TEMPLATED SYNTHESIS OF

MEDIUM HETEROCYCLES

M Rubin M Rubina A Edwards P Ryabchuk

University of Kansas Department of Chemistry

A highly efficient diastereocenvergent reaction of bromocyclopropanes with various nucleophiles

have been recently developed in our laboratories1-7

This reaction involves a base-assisted

dehydrohalogenation to produce a highly reactive cyclopropene intermediate which undergoes

subsequent nucleophilic addition across the strained C=C bond Different intramolecular modes of

this reaction will be presented Possibilities for assembly of heterocyclic scaffolds with various ring

sizes including enantiomerically pure medium heterocycles will be demonstrated The mechanistic

aspect of this transformation and the means of controlling its diastereoselectivity will be discussed

Br

Nu

R

O

N O HN

O

R

R

Me

O

BaseTHF

18-crown-6 (cat)

t-BuOKTHFKOHTHF

t-BuOK DMSO

Ar Me

O

N

R

O

H

H

8-membered 7-10-membered

8-9-membered

N

Ph

Ph

O

t-BuOK THF

5-membered

O

O

R

R8-membered

O

O

O

Me

NH

HNO

Me

15-memberedt-BuOK DMSO

t-BuOK THF

References

[1] Alnasleh B K Sherrill W M Rubina M Banning J Rubin M J Am Chem Soc 2009

131 6906-6907

[2] Banning J E Prosser A R Rubin M Org Lett 2010 12 1488-1491

[3] Prosser A R Banning J E Rubina M Rubin M Org Lett 2010 12 3968-3971

[4] Banning J E Prosser A R Alnasleh B K Smarker J Rubina M Rubin M J Org

Chem 2011 76 3968-3986

[5] Ryabchuk P Rubina M Xu J Rubin M Org Lett 2012 14 1752-1755

[6] Banning J E Gentillon J Ryabchuk P Prosser A R Rogers A Edwards A Holtzen

A Babkov I A Rubina M Rubin M J Org Chem 2013 78 7601-7616

[7] Ryabchuk P Edwards A Gerasimchuk N Rubina M Rubin M Org Lett 2013 15

6010-6013

75

OC14

THE STRATEGY FOR ATOM ECONOMICAL REDUCTIVE ADDITION

DEOXYGENATION

D Chusov PN Kolesnikov VI Maleev NZ Yagafarov

ANNesmeyanov Institute of Organoelement Compounds of Russian Academy of Sciences

Herein we present the concept of using carbon monoxide for atom economical reductive addition

deoxygenation without external hydrogen source [1] We are utilizing this idea by showing that N-

H and C-H bonds of the reagents could be used as hydrogen source (Fig 1)

Figure 1

References

D Chusov B List Angew Chem Int Ed 2014 53 DOI 101002anie201400059

76

OC15

DINUCLEAR CATALYSIS ACCELERATED METAL-DEPENDENT RING-

OPENING POLYMERIZATION OF LACTIDE

E Kirillov

Universite de Rennes 1 UMR 6226 - CNRS 35042 Rennes France

Multinuclear olefin polymerization catalysts (incorporating several active metal centers in one and

the same molecule) have recently emerged as a distinct and brand new class of molecular catalysts 1

Implicit cooperative behavior2 of two or more metal centers in active species of these systems can

contribute to enhanced performance (with respect to mononuclear analogues) in terms of activity

chain-transfer kinetics and also monomers selectivity in copolymerization reactions

Dinuclear complexes of aluminum and indium with a bis(phenoxy-imine) platform have been

synthesized and used in the polymerization of lactide3a

Kinetic studies demonstrated that the

dialuminum precursor (Scheme 1) provides a more favorable reaction pathway in terms of

activation free energy than that of directly related monoaluminum systems3b

No similar trend was

observed with the corresponding diindium monoindium systems which was attributed to a

dissimilar ROP mechanism Details of the mechanisms and key factors of the dinuclear catalysis

will be discussed

Scheme 1 A dinuclear aluminum system enables a 5-to-10 fold boost in activity when compared to

its monoaluminum analogues

1 Delferro M Marks T J Chem Rev 2011 111 2450

2 Bratko I Goacutemez M Dalton Trans 2013 42 10664

3 (a) Normand M Roisnel T Carpentier J-F Kirillov E Chem Commun 2013 49 11692

(b) Normand M Dorcet V Kirillov E Carpentier J-F Organometallics 2013 32 1694

77

OC16

RECENT METHODOLOGICAL DEVELOPMENTS FOR THE QUANTUM

CHEMICAL STUDY OF COMPLEX SYSTEMS

S Irle

Nagoya University Department of Chemistry Nagoya Japan

The structural complexity of molecular clusters increases with size due to the associated rapidly

growing configuration space Two examples are realized in i) the transition from molecular to bulk

systems and ii) in the simulation of extended biosystems In such systems traditional quantum

chemical approaches of investigations are hampered by the vastly increasing computational cost

even considering ever-growing supercomputer capabilities Computationally inexpensive yet

accurate schemes such as the density-functional tight-binding (DFTB) method [1] and there linear

scaling versions promise here a significant advantage

We have recently engaged in developing novel methodologies for systems with increasing

structural complexity driven by motivation from experimental studies In this presentation we will

review a) the Kick-fragment-based ldquoKick3rdquo conformationally aware approach for studying

molecular [2] and ionic liquid clusters with increasing size and our implementation of the fragment

molecular orbital (FMO) method [3] with DFTB called ldquoFMO-DFTBrdquo in the popular GAMESS-

US quantum chemistry package [4] The computational effort of the method scales nearly linearly

with system size with a negligible pre-factor and allows the efficient massively-parallel quantum

chemical geometry optimization and direct molecular dynamics (MD) simulations of systems

containing several tens of thousands of atoms in particular when fragments consist of units with

less than 50 atoms [5] The method should be particularly useful to predict structures of new

artificial peptides and proteins predict enzymatic reaction pathways estimate free energy

contributions along pathways where large parts or even the entire protein including surrounding

water is treated quantum chemically and to simulate the effects of highly polarizable andor

charged solvents in explicit-solvent MD simulations

Unlike other linear scaling schemes such as divide and conquer approaches (DC) FMO-DFTBs

very design allows the insightful decomposition of interaction energies between ligands and

proteins in terms of electrostatics exchange-repulsion charge transfer dispersion and solvent

screening contributions in a straightforward manner

[1] M Gaus Q Cui M Elstner J Chem Theory Comput 7 931 (2011)

[2] M A Addicoat S Fukuoka A J Page S Irle J Comput Chem 34 2591 (2013)

[3] D G Fedorov T Nagata K Kitaura Phys Chem Chem Phys 14 7562 (2012)

[4] M W Schmidt K K Baldridge J A Boatz S T Elbert M S Gordon J H Jensen S

Koseki N Matsunaga K A Nguyen S Su T L Windus M Dupuis and J A Montgomery

Jr J Comput Chem 1993 14 1347 httpwwwmsgameslabgovgamessindexhtml

[5] Y Nishimoto D G Fedorov S Irle submitted

78

OC17

QUANTUM CHEMICAL MODELING IN STUDIES OF MOLECULAR

MECHANISMS OF ENZYME CATALYSIS

AV Nemukhin

Chemistry Department MV Lomonosov Moscow State University Moscow 199991 Russia NM

Emanuel Institute of Biochemical Physics Russian Academy of Sciences Moscow Russia

Recent results [1-3] of modeling chemical transformations in enzyme active sites using quantum-

based approaches will be discussed We apply quantum mechanicsmolecular mechanics (QMMM)

approaches to compute minimum energy pathways connecting enzyme-substrate and enzyme-

product complexes Appropriate crystal structures from the Protein Data Bank usually serve as a

source of coordinates of heavy atoms to create molecular model systems After in silico

construction of a three-dimensional full-atom model evolution of the model system along carefully

selected reaction coordinates is analyzed

Several examples of such modeling will be presented The complete cycle of chemical

transformations in penicillin acylase a unique enzyme that belongs to the recently discovered

superfamily of N-terminal nucleophile hydrolases with its most specific substrate penicillin G

leading to formation of 6-aminopenicillanic and phenylacetic acids [1] will be presented Keton-

ketal transformations at the active site of matrix metalloproteinases characterized computationally

[2] may be explored to propose specific inhibitors Chemical reactions in photoreceptor proteins

constitute an active field of application of QMMM modeling the case of BLUF domains will be

discussed [3]

Simulation results of guanosine triphposphate hydrolysis (GTP) by small GTPases icluding Ras

protein will be in focus According to newly obtained data the molecular events of the chemical

steps upon GTP hydrolysis include (i) cleavage of the phosphorus (Pγ) -oxygen bond in GTP upon

approach of the properly aligned catalytic water molecule producing GDP (ii) formation of a new

chemical bond between phosphorus and oxygen of water (iii) redistribution of protons between

reacting species leading to inorganic phosphate Pi

References

[1] Grigorenko BL Khrenova MG Nilov DK Nemukhin AV Švedas VK Catalytic Cycle of

Penicillin Acylase from Escherichia coli QMMM Modeling of Chemical Transformations in

the Enzyme Active Site upon Penicillin G Hydrolysis ACS Catal 2014 V 4 P 2521ndash2529

[2] Khrenova MG Nemukhin AV Savitsky AP Computational Characterization of Ketone-

Ketal Transformations at the Active Site of Matrix Metalloproteinases J Phys Chem B 2014

V 118 P 4345-4350

[3] Khrenova MG Nemukhin AV Domratcheva T Photoinduced Electron Transfer Facilitates

Tautomerization of the Conserved Signaling Glutamine Side Chain in BLUF Protein Light

Sensors J Phys Chem B 2013 V 117 P 2369-2377

79

OC18

EXCITED STATES AND MOLECULAR INTERACTIONS IN PROTEINS

AND SOLUTIONS

JH Hasegawa

Catalysis Research Center Hokkaido University Sapporo Japan

Solvatochromism and fluorescent solvatochromism are well-known phenomena and there are rich

accumulations in experimental publications Color tuning in proteins such as human color vision

and fluorescent proteins could be also classified to solvatochromism but with a specific

environment where anisotropic molecular interactions play important roles

We have studied biological color tuning with the SAC-CIMM calculations in which MM

description was adopted for the environmental effect This classical description for the environment

works very well for explaining the color tuning mechanisms

In some cases however environmental electronic structure effect becomes important To

investigate the origin of the QM effect we propose a scheme based on the wave function theory

with a MO localization scheme The role of the environmental electronic effect was analyzed in

terms of amino acidsrsquo orbital delocalizations excitonic interactions excited-state polarization and

dispersion interactions In the presentation we would show some results of pilot applications

80

OC19

CATIONIC GOLD-CATALYZED HETEROANNULATIONS

EV Van Der Eycken

University of Leuven (KU Leuven) Department of Chemistry Leuven Belgium

Gold catalysis is one of the fast growing research topics of modern organic chemistry In this

context gold-catalyzed carbocyclization and heteroannulation strategies have recently attracted

much attention due to the selective and efficient activation of the C-C triple bond towards a wide

range of nucleophiles Moreover the combination of multicomponent reactions with gold catalysis

gives access to complex molecular architectures in few steps as compared to traditional multistep

processes We will comment on our recent findings in this field A concise route to indoloazocines1

via a sequential Ugigold-catalyzed intramolecular hydroarylation2 will be presented A diversity-

oriented approach to spiroindoles via a post-Ugi gold-catalyzed diastereoselective domino

cyclization3 will be described (Scheme) as well as a regioselective approach for the synthesis of

pyrrolopyridinones and pyrroloazepinones employing a gold(I)platinum(II) switch4

N

O R3

H2N

R4

COOHR5

NC+

i) Ugi-4CR

NN

N

R5

O

O R3

(+-)

H

R1

R2

R2

R4

R1ii) cationic gold rt

13 examplesup to 80 yield

References

1 Synthesis of Azocino[54-b]indoles via Au-Catalyzed Intramolecular Alkyne Hydroarylation V

A Peshkov O P Pereshivko E V Van der Eycken Adv Synth Cat 354 2841-2848 2012

2 Concise route to indoloazocines via a sequential Ugigold-catalyzed intramolecular

hydroarylation S G Modha D D Vachhani J Jacobs L Van Meervelt E V Van der

Eycken Chem Commun 48 (52) 6550ndash6552 2012

3 Diversity-Oriented Approach to Spiroindolines Post-Ugi Gold-Catalyzed Diastereoselective

Domino Cyclization S G Modha A Kumar D D Vachhani J Jacobs S K Sharma V S

Parmar L Van Meervelt E V Van der Eycken Angew Chem Int Ed 51 9572-9575 2012

4 Gold(I) and Platinum(II) switch A post-Ugi intramolecular hydroarylation to pyrrolopyridinones

and pyrroloazepinones S G Modha A Kumar D D Vachhani S K Sharma V S Parmar E

V Van der Eycken Chem Comm 48 10916-10918 2012

81

OC20

Pd-SUPPORTED BIMETALLIC COMPOSITIONS FOR

STEREOSELECTIVE LIQUID PHASE SEMI-HYDROGENATION OF

DIPHENYLACETYLENE

IS Mashkovsky1 AV Sergeeva

1 OV Turova

1 MN Vargaftik

2 NYu Kozitsyna

2 AYu

Stakheev1

1 - Zelinsky Institute of Organic Chemistry RAS Moscow Russia

2 - Kurnakov Institute of General and Inorganic Chemistry RAS Moscow Russia

This study was focused on the development of the efficient catalyst for selective semi-

hydrogenation of internal alkene Diphenylacetylene (DPA) was used as a model compound The

catalytic compositions based on Pd-Zn Pd-Co Pd-Ni were investigated The samples were

prepared via two techniques (1) on the basis of palladium acetate heterobimetallic complexes as

precursors and (2) using traditional co-impregnation by individual metal salts It was found that the

systems based on bimetallic acetate complexes exhibited a substantial increase in selectivity to

alkene and cis-isomer formation at high conversion of the parent alkyne (DPA) albeit at the

expense of some decrease in the activity The detailed physicochemical study with TEM-EDS

SEM-EDS EXAFS and IR-spectroscopy reveals that the use of heterobimetallic acetate complex as

a precursor allows us to avoid metallic phase segregation during the reduction treatment of the

catalyst which ensures high homogeneity of bimetallic particles and leads to enhanced selectivity

Financial support was provided by RFBR foundation grants 12-03-31487 13-03-12176

Рис 1 Dependency of selectivity to cis-isomer and alkene on DPA conversion for PdAl2O3

catalyst modified with Co Zn and Ni in liquid phase DPA hydrogenation

Se

lecti

vit

y t

o c

is-i

so

me

r

0

10

20

30

40

50

60

70

80

90

100

70 80 90 100

0

10

20

30

40

50

60

70

80

90

100

70 80 90 100

DPA conversion

093PdAl2O3

093Pd-052ZnAl2O3

093Pd-053NiAl2O3

093Pd-053CoAl2O3

DPA conversion

Se

lecti

vit

y t

o a

lke

ne

H

H

H

H

H

H

+

H

H

H

H

+

093PdAl2O3

093Pd-052ZnAl2O3

093Pd-053NiAl2O3

093Pd-053CoAl2O3

82

OC21

DESIGN OF NANOSTRUCTURES ON THE BASIS OF TWO

PHARMACOPHORIC FRAGMENTS - FULLERENE AND PIPERIDINE

DERIVATIVES

GV Grishina IS Veselov IV Trushkov

M V Lomonosov Moscow State University Department of Chemistry

This communication is described the creation of a new nanobiosystems with high antivirus potential

based on the two pharmacophoric fragments - derivatives of fullerene C60 and piperidine ligands

Design of nanoadditive on the basis of two pharmacophoric fragments - functional derivatives of

trans-34-dihydroxypiperidine and organically modified by fullerene C60 can be a very promising

bioactive substances Such a perspective is related to using first as ligands several trans-34-

dihydroxylated piperidines already demonstrated anti-HIV activity and secondly the uniqueness of

fullerene spheroid significantly reduce the toxicity of biologically active adducts We believed that

binding of two biologically active units in the same system will be very useful and promising

N

YX

COOEtON

Me NY

X

1 X = H Y = OH

2 X = Y = OH

3 X =NHR Y = OH

4

Monoadducts 1-4 have obtained by the Benguel and Prato reactions respectively and have since

received 12 new fullerene adducts based on the derivatives of the trans-34-dihydroxypyridine and

trans-4-amino-3-hydroxypiperidines Isolation and identification of these adducts were made using

column and preparative chromatography on silica gel structure and stereochemistry were

established with the involvement required in each case spectral methods including mass

spectrometry and МАLDI X-ray analysis and 1H

13C NMR The main difficulty in undertake

researches consisted of significant differences reactivity due to high lipophilicity derivatives of

fullerene and high hydrophilicity piperidine ligands To reduce this difference we have modified

both fragments introduction to piperidine ligands andor in the molecule organically modified

fullerenes functions andor linkers which facilitated further obtaining of target adducts For some

samples of adducts managed to get soluble in alcohol salts A very important factor has been the

elucidation of the impact of structural and stereochemical factors on possible synergies in the

adduct investigation Target adducts are a new type of nanostructures for medical chemistry with

great pharmacological potential

83

OC22

CHIRASAC STUDY ON CHIRAL SPECTROSCOPY AND PHOTOBIOLOGY

H Nakatsuji T Miyahara

Quantum Chemistry Research Institute (QCRI) 1-36 Goryo-Oohara Nishikyo-ku Kyoto 615-8245

Japan

Weak interactions of molecules with solvents andor environments are of crucial importance in

material science and biology but rather difficult to investigate quantitatively Circular dichroism

(CD) spectra reflect sensitively the conformational structures of chiral molecules their (weak)

interactions with solvents andor proteins etc The SAC-CI method gives their CD spectra very

reliably From this fact the SAC-CI method is a useful tool to investigate the conformational

geometries of chiral molecules their interactions with environments etc by comparing their

experimental and SAC-CI theoretical CD spectra We initiated a systematic molecular technology

called ChiraSac (Chirality + SAC-CI) project (see Figure 1) by using the SAC-CI code and other

highly reliable and useful codes on ldquoGAUSSIANrdquo suit of programs [1] We have already applied

this project successfully to several topics of chiral spectroscopy and photobiology [2-4] We will

present here conformational dependence of α-Hydroxyphenylacetic Acid and similarities and

differences between RNA and DNA etc as some recent applications of ChiraSac to chiral

spectroscopy and photobiology

References

[1] M J Frisch G W Trucks H B Schlegel G

E Scuseria M A Robb J R Cheeseman G

Scalmani V Barone B Mennucci G A

Petersson et al Gaussian 09 Gaussian Inc

Wallingford CT 2009

[2] Circular Dichroism Spectra of Uridine

Derivatives ChiraSac Study Tomoo

Miyahara Hiroshi Nakatsuji and Takehiko

Wada J Phys Chem A 118 2931-2941

(2014)

[3] Conformational Dependence of the Circular

Dichroism Spectrum of α-Hydroxyphenyl-

acetic Acid A ChiraSac Study Tomoo

Miyahara and Hiroshi Nakatsuji J Phys

Chem A 117 14065- 14074 (2013)

[4] Helical Structure and Circular Dichroism

Spectra of DNA A Theoretical Study T

Miyahara H Nakatsuji and H Sugiyama J

Phys Chem A 117 42-55 (2013)

84

OC23

A DFT ANALYSIS ON THE ELECTRONIC PROPERTIES OF

METHYLAMMONIUM LEAD IODIDE PEROVSKITE

K Yamashita1 G Giorgi

1 J Fujisawa

2 H Segawa

2

1 - Department of Chemical System Engineering The University of Tokyo Japan

2 - Research Center for Advanced Science and Technology The University of TokyoJapan

Methylammonium (MA) lead iodide perovskite (CH3NH3PbI3) plays an important role in light

absorption and carrier transport in efficient organicminusinorganic perovskite solar cells [1] In my talk

the first theoretical estimation of effective masses of photocarriers and the role of MA cation in

CH3NH3PbI3 will be discussed

Spin-polarized DFT calculations have been performed with the generalized gradient approximation

From the charge density of the two-fold degenerate states ((a) and (b)) of CBM and those ((c) and

(d)) of VBM one can see that photogenerated electrons around CBM and holes around VBM exist

separately results related to the ambipolar transport nature of the material Effective masses of

photogenerated electrons and holes are estimated to be me =023m0 and mh = 029m0

respectively including spinminusorbit coupling (SOC) effects This result is consistent with the long-

range ambipolar transport property and with the larger diffusion constant for electrons compared

with that for holes in the perovskite which enable efficient photovoltaic conversion [2]

We also have focused our attention on the MA cation and studied the role it plays in the

electronicoptical features of the perovskite paying attention mainly to the iodide compound [3] A

comparison is performed between the electronic properties of MAPbI3 organic-inorganic perovskite

and those of the purely inorganic CsPbI3

References 1 J Bisquert J Phys Chem Lett 4 2597 (2013)

2 G Giorgi J Fujisawa H Segawa K Yamashita J Phys Chem Lett 4 4213 (2013)

3 G Giorgi J Fujisawa H Segawa K Yamashita J Phys Chem 118 12176 (2014)

85

OC24

A HYBRID MCMD REACTION METHOD WITH RARE EVENT-DRIVING

MECHANISM ATOMISTIC REALIZATION OF 2-CHLOROBUTANE

RACEMIZATION PROCESS IN DMS SOLUTION

M Nagaoka

Graduate School of Information Science Nagoya University Furo-cho Chikusa-ku Nagoya 464-

8601 Japan Core Research for Evolutional Science and Technology (CREST) Japan Science and

Technology Agency (JST) Honmachi Kawaguchi 332-0012 Japan ESICB Kyoto University

Kyodai Katsura Nishikyo-ku Kyoto 615-8520 Japan

We demonstrate a new efficient hybrid MCMD reaction method with a rare event-driving

mechanism as a practical lsquoatomisticrsquo molecular simulation of large-scale chemically reactive

systems (Figure 1) Application of the method to (R)-2-chlorobutane molecules in NN-

dimethylformamide (DMF) molecules starting in the optical pure state (100 ee) was found to

successfully provide such an atomistic state with ~0 ee the expected purity of (R)- to (S)-

enantiomers of the racemic mixture in chemical equilibrium [1]

This hybrid MCMD reaction method is promising for studies of various properties in chemically

reactive systems [2] and their stereochemistry as well

Figure 1 Schematic representation of the hybrid MCMD reaction method The curly curves

represent the molecular dynamical (MD) moves in phase space following the equations of motion

while the straight lines with arrows represent the Monte Carlo (MC) moves (or transitions) of the

system (right figure) whose dynamical moves would be extremely rare events In the left figure the

configurational distribution in equilibrium peq

is proportional to the exponential factor exp[-βU]

where U is the global potential function The right figure shows regional distributions eg preq

exp[-βUr] in region r etc The connecting points of the two kinds of moves (open circles) are

selected according to the criteria for chemical reaction occurrence Note that they do not represent

real connections since these points correspond to almost identical states in configuration space but

not in momentum space and with different configurational gradients Wrrarrs and Wsrarrt are the

transition probabilities from state r to s and from s to t respectively [1]

[1] Masataka Nagaoka Yuichi Suzuki Takuya Okamoto Norio Takenaka Chem Phys Lett 583

80 (2013)

[2] N Takenaka Y Suzuki H Sakai M Nagaoka J Phys Chem C 118 10874 (2014)

Local Organizing Committee

ND Zelinsky Institute of Organic Chemistry RAS

M P Egorov Chairman

V P Ananikov Vice-chairman

A D Dilman

A M Sakharov

A Y Stakheev

AM Starosotnikov

A O Terentev

O V Turova

S G Zlotin

National Advisory Committee

G A Abakumov N Novgorod

I P Beletskaya Moscow

Y N Bubnov Moscow

V N Charushin Ekaterinburg

O N Chupakhin Ekaterinburg

A I Konovalov Kazan

V V Lunin Moscow

V I Minkin Rostov

O M Nefedov Moscow

V N Parmon Novosibirsk

O G Syniashin Kazan

V A Tartakovsky Moscow

B A Trofimov Irkutsk

M S Yunusov Ufa

N S Zefirov Moscow

Index

Plenary Lectures 7

Invited Lectures 22

Oral Communications 60

Posters 110

Authors Index 326

7

Plenary Lectures

8

9

PL1

THE APPLICATION OF PHOTOREDOX CATALYSIS TO NEW

TRANSFORMATIONS IN CHEMICAL SYNTHESIS

DWC MacMillan

Merck Center for Catalysis Princeton UniversityPrinceton NJ 08544

This lecture will discuss the advent and development of new concepts in chemical synthesis

specifically the combination of photoredox catalysis with organic catalysis This new approach to

ldquosynergistic catalysisrdquo will demonstrate that multiple yet separate catalytic cycles can be aligned to

generate activated intermediates that rapidly combine with each other thereby allowing new

approaches to enantioselective CndashC and C-heteroatom bond formation

We will also introduce an approach to the discovery of new chemical reactions that we term

accelerated serendipity Accidental or lsquoserendipitousrsquo discoveries have led to some of the most

important breakthroughs in scientific history many of which have directly affected human life

Given our overarching goal of developing fundamentally new and useful chemical transformations

using catalysis and by acknowledging the tremendous impact of serendipity in scientific discovery

we questioned whether this phenomenon could be forced or simulated and therefore employed as a

tool for reaction discovery

In this presentation we will describe several new transformations that have been discovered via

ldquoaccelerated serendipityrdquo that we expect will find widespread adoption throughout the field of

chemical synthesis Moreover we will further describe how mechanistic understanding of these

processes has led to the design of a valuable new yet fundamental chemical transformation

Acknowledgements Financial support was provided by NIHGMS (R01 01 GM093213-01) and kind gifts from Merck

Amgen and Abbott

10

PL2

GOLD CATALYSIS 20

ASK Hashmi

Organisch-Chemisches Institut Fakultaumlt fuumlr Chemie und Geowissenschaften Universitaumlt

Heidelberg Im Neuenheimer Feld 270 69120 Heidelberg Germany

Homogeneous catalysis by gold has developed to an important sector of catalysis research1

Initially efforts in methodology development clearly dominated in the last years also an increasing

number of applications in synthesis has been reported23

Efforts to understand the basic mechanism

of these reactions continuously accompanied the field4

For twelve years most of the reactions followed simple reaction mechanisms basing on the

interaction of one gold centre in a gold complex or organogold compound with the substrate

molecule In most of these reactions vinylgold or alkylgold intermediates are involved sometimes

also gold carbenoids

Now an entirely new family of reactions basing on the activation of the organic substrates by two

gold complexes at the same time (one -coordinated the other -coordinated) has been discovered

These open up entirely new synthetic possibilities and follow quite complex mechanisms These

mechanisms which are new to the field of organometallic chemistry will be discussed in detail

Some of the new reactions even allow positional selective CH activations of alkyl side chains as

exemplified below

The presentation will also contain results from computational chemistry

References

1 A S K Hashmi Chem Rev 2007 107 3180-3211

2 A S K Hashmi M Rudolph Chem Soc Rev 2008 37 1766-1775

3 M Rudolph A S K Hashmi Chem Soc Rev 2012 41 2448-2462

4 A S K Hashmi Angew Chem Int Ed 2010 49 5232-5241

11

PL3

HOW MUCH CATALYST DO WE NEED

C Bolm

Institute of Organic Chemistry RWTH Aachen University 52056 Aachen Germany

Various C-N- C-O- and C-C-bond forming reactions leading to cross coupling-type products can

be performed without transition metals In this presentation we will discuss cyclizations affording

benzimidazol-2-ones1 and indazoles

2 (eqs 1 and 2 respectively) Photochemical initiations (eq 3)

led us to other directions34

R1 X

NHN

O

R3

R2

N

N

R2

R3

R1

O

40 degC 24 h

X = I Br (Cl F)

(eq 1)

toluene RT 25 h

N

R2

HNR3X

N

N

R2

R3

R1 R1

TMS

O

R2

O

R1hn

CH2Cl2 RT O

O

R1R2

TMS

X = I Br

(eq 2)

(eq 3)

KOHDMSO

diamineK2CO3

Finally we will present mechanochemical activations in ball mills that allow reducing the catalyst

loadings in asymmetric organocatalyses5-7

References

1 a) Yuan Y Thomeacute I Kim S H Chen D Beyer A Bonnamour J Zuidema E Chang

S Bolm C Adv Synth Catal 2010 352 2892 b) Beyer A Reucher C M M Bolm C

Org Lett 2011 13 2876 c) Thomeacute I Bolm C Org Lett 2012 14 1892 d) Beyer A

Buendia J Bolm C Org Lett 2012 14 3948 e) Baars H Beyer A Kohlhepp S V Bolm

C Org Lett 2014 16 536

2 Thomeacute I Besson C Kleine T Bolm C Angew Chem Int Ed 2013 52 7509

3 a) Zhang H-J Becker P Huang H Pirwerdjan R Pan F-F Bolm C Adv Synth Catal

2012 354 2157 b) Becker P Priebbenow D L Zhang H-J Pirwerdjan R Bolm C J

Org Chem 2014 79 814 c) Becker P Priebbenow D L Pirwerdjan R Bolm C Angew

Chem Int Ed 2014 53 269

4 For a photochemical activation in a metal catalysis see Bizet V Buglioni L Bolm C

Angew Chem Int Ed DOI 101002anie201310790

5 a) Joumlrres M Mersmann S Raabe G Bolm C Green Chem 2013 15 612 See also in b)

Kleine T Buendia J Bolm C Green Chem 2013 15 160

6 For a video see httpwwwbeilsteintvtvpostasymmetric-organocatalysis-in-a-ball-mill

7 For a general overview see James S L Collier P Parkin I Hyett G Braga D Maini L

Jones B Friscic T Bolm C Krebs A Mack J Waddell D C Shearouse W C Orpen

G AdamsC Steed J W Harris K D M Chem Soc Rev 2012 41 413

12

PL4

ldquoMOLECULAR METATHESIS CATALYSTSrdquo AT THE DAWN OF

INDUSTRIAL IMPLEMENTATION

DE Fogg

University of Ottawa

Ruthenium-catalyzed olefin metathesis has enormous potential for impact on the chemical

enterprise in sectors ranging from pharma to specialty polymers and ldquogreenrdquo feedstocks

Phosphine-free metathesis catalysts particularly those of the Hoveyda type (HII see Figure 1)

occupy a position of increasing prominence In one of the most high-profile current applications of

metathesis chemistry transformation of seed oils into functionalized olefins HII significantly out-

performs the benchmark Grubbs catalyst GII [12]

despite the fact that the two catalysts generate a

common active species (A) Reports from pharma RampD indicate that HII also offers superior

performance in some demanding RCM applications (RCM = ring-closing metathesis)[3]

As these

and closely related molecular metathesis catalysts enter deployment in process chemistry

understanding the mechanistic basis of their performance takes on added importance

We will discuss potential contributors to the improved productivity of HII the absence of free

PCy3 the presence of the styrenyl ether ligand and operation of HII via interchange-associative

pathways The relevance of each of these factors will be considered in the context of demanding

ring-closing and cross-metathesis reactions

Figure 1 Molecular structure of an organometallic product

References

[1] Miao X Fischmeister C Dixneuf P H Bruneau C Dubois J L Couturier J L Green

Chem 2012 14 2179-2183

[2] Biermann U Bornscheuer U Meier M A R Metzger J O Schafer H J Angew Chem

Int Ed 2011 50 3854ndash3871

[3] van Lierop B J Lummiss J A M Fogg D E Ring-Closing Metathesis A How-To Guide

In Olefin Metathesis Theory and Practice Grela K Ed Wiley Weinheim 2014

13

PL5

REDUCTIONS WITH ORGANIC REAGENTS mdash THE ELECTRON AS A

CATALYST

A Studer

WWU Muenster Chemistry Germany

In the lecture reduction processes for generation of various radicals using different organic reagents

will be presented Reactions are generally conducted using stoichiometric SET-reagents However

also some catalytic variants will be presented In the presentation radical perfluoroalkylations and

azidations will be addressed Moreover the concept of using the electron as a catalyst will be

discussed and some examples provided

14

PL6

NANOELECTRONICS MOLECULAR METAL WIRES AND RELATED

MOLECULAR MATERIALS

SM Peng

Department of Chemistry National Taiwan University Taipei Taiwan

We have designed a series of new ligands such as oligo-α-pyridylamines and used them to

construct an unique class of quadruple helix of metal strings This achievement leads to a new

direction to the application of molecular wires in the nanoelectronics

The outline is as follows

I Linear Metal String Complexes (1)

Synthesis Structure Bonding

II Potential Application as Molecular Metal Wires amp Molecular Switches (2)

STM-bj Study on the Conductivity of Metal Strings

Comparative Study on the I-V Characterisics (Theory VS Experiment)

III Tuning of the Metal Strings (3-9)

Naphthyridyl Amino Ligands Low Oxidation Mixed Metal Strings

Asymmetrical Ligands Toward Molecular Rectifier

Heteronuclear Metal String Complexes

Chiral Quadruple Helixes

IV Conclusion

Fig1 Metal Strings of Oligo- -pyridylamido Ligands

1 C-Y Yeh C-C Wang Y-H Chen and S-M Peng in Redox Systems Under Nano-Space

Control Ed T Hirao Springer Germany 2006 Ch 5

2 I-W P Chen M-D Fu W-H Tseng J-Y Yu S-H Wu C-J Ku C-H Chen and S-M

Peng Angew Chem Int Ed Engl 2006 5414

3 (a) C-H Chien J-C Chang C-Y Yeh G-H Lee J-M Fang and S-M Peng Dalton Trans

2006 2106 (b) C-H Chien G-H Lee Y Song and S-M Peng Dalton Trans 2006 3249

4 M-M Rohmer I P-C Liu J-C Lin M-J Chiu C-H Lee G-H Lee M Benard X Lopez

S-M Peng Angew Chem Int Ed Engl 2007 46 3533

5 I P-C Li W-Z Wang and S-M Peng Chem Commun 2009 4323-4331

6 R H Ismayilov W-ZWang G H Lee C Y Yeh S A Hua Y Song M M Rohmer M

Beacutenard S-M Peng Angew Chem Int Ed 2011 50 2045-2048

7 I P-C Liu C-H Chen S-M Peng Bull Jpn Soc Coord Chem 2012 59 1-8

N N N N N

M M M M MX X

4

m

M = N i C o C r

m = 0 1 2 3

X = C l N C S

15

8 M-C Cheng C-L Mai C-Y Yeh G-H Lee S-M Peng Chem Commun 2013 49 7938-

7940

9 M-J Huang S-A Hua M-D Fu G-C Huang C Yin C-H Ko C-K Kuo C-H Hsu G-H

Lee K-Y Ho C-H Wang Y-W Yang I-C Chen S-M Peng C-h Chen Chem Eur J

2014 DOI 101002chem201400067

16

PL7

NEW CYCLOADDITION STRATEGIES BASED ON STRAINED AND

UNUSUAL MOLECULES

RL Danheiser

Department of Chemistry Massachusetts Institute of Technology Cambridge MA 02139 USA

Highly substituted carbocyclic and heterocyclic rings are key structural features in many

biologically significant and commercially important compounds Although classical synthetic

approaches to such compounds have generally relied on linear substitution strategies convergent

cycloaddition and annulation strategies have emerged as powerful alternative methods for the

assembly of highly substituted cyclic compounds The intrinsic convergent nature of cycloaddition

and annulation strategies facilitates the efficient assembly of highly substituted systems that would

have required long multistep routes using alternative methods

This talk will focus on the application of strained and unusual molecules as building blocks in

cycloaddition strategies for the construction of complex carbocyclic and heterocyclic compounds

The synthetic utility of highly unsaturated conjugated molecules such as vinylketenes conjugated

enynes vinylallenes allenylimines and iminoacetonitriles will be described as well as their

application in the total synthesis of natural products

17

PL8

SILICON TETHER MOTIF IN C-H ACTIVATION REACTIONS

V Gevorgyan

University of Illinois at Chicago

We have developed a set of new transition metal-catalyzed C-H activation methodologies

employing a silicon-tether motif These methods feature (a) use of silyl group as a tether between a

substrate and a reagent thus transforming intermolecular reaction into intramolecular reaction1-2

(b) employment of a silicon-tethered directing group which is traceless or easily convertable into

valuable functionalities3-8

(c) use of silyl-tethered hydrosilane reagent9-10

and (d) introduction of

new NSi-chelation concept that allows for a remote activation of aliphatic C-H bonds11

The scope of these transformations will be demonstrated and the mechanisms will be discussed

References

1 Huang C Gevorgyan V J Am Chem Soc 2009 131 10844

2 Huang C Gevorgyan V Org Lett 2010 12 2442

3 Chernyak N Dudnik A S Huang C Gevorgyan V J Am Chem Soc 2010 132 8270

4 Dudnik A S Chernyak N Huang C Gevorgyan V Angew Chem Int Ed 2010 49 8729

5 Huang C Chattopadhyay B Gevorgyan V J Am Chem Soc 2011 133 12406

6 Huang C Ghavtadze N Chattopadhyay B Gevorgyan V J Am Chem Soc 2011 133 17630

7 Gulevich A V Melkonyan F S Sarkar D Gevorgyan V J Am Chem Soc 2012 134

5528

8 Sarkar D Melkonyan F S Gulevich A V Gevorgyan V Angew Chem Int Ed 2013 52

10800

9 Kuznetsov A Gevorgyan V Org Lett 2012 14 914

10 Kuznetsov A Onishi Y Inamoto Y Gevorgyan V Org Lett 2013 15 2498

11 Ghavtadze N Melkonyan F S Gulevich A Huang C Gevorgyan V Nat Chem 2014 6

122

18

PL9

WERNER COMPLEXES A NEW CLASS OF CHIRAL HYDROGEN BOND

DONOR CATALYSTS FOR ENANTIOSELECTIVE ORGANIC REACTIONS

JA Gladysz

Department of Chemistry Texas AampM University PO Box 30012 College Station Texas 77842-

3012 USA

Salts of the chiral tris(ethylenediamine)-substituted octahedral trication [Co(en)3]3+

and related

species have played important historical roles in the development of inorganic chemistry and

stereochemistry12

As Werner described in 1912 the two enantiomers commonly designated and

can be separated by crystallization of the diastereomeric tartrate salts2 However despite the low

cost and ready availability of the building blocks there have been no applications in

enantioselective organic synthesis

NH2

NH2

H2N

H2N

NH2

H2N

Co3+

H2N

H2N

NH2

NH2

NH2

H2N

Co3+L D

We have found that [Co(en)3]

3+ and related cations can be rendered soluble in organic solvents by

using lipophilic anions such as BArfndash

3 Suitably functionalized derivatives act as highly

enantioselective catalysts for a variety of carbon-carbon bond forming reactions The mechanisms

involve outer sphere activation of the electrophile by hydrogen bonding to the NH moieties Other

types of metal-containing chiral hydrogen bond donors are also effective including a chelate of the

CpRuL fragment

H2N

H2N

NH2

NH2

NH2

H2N

Co3+ Ph

Ph

Ph

Ph

Ph

Ph

2Clndash BAr fndash

catNO2

NO2

OMe

O

MeO

O

Et3N acetone

10 molO O

OMeMeO

12 eq 0 degCX

X

Time (h)

Conversion ()

ee ()

15 gt99 88NO2

OMe

O

MeO

O

22 98 94NO2

OMe

O

MeO

O

O

Ph

H2N

H2N

NH2

NH2

NH2

H2N

Co3+ Ph

Ph

Ph

Ph

Ph

Ph

2BF4ndash BAr f

ndash

H2N

H2N

NH2

NH2

NH2

H2N

Co3+ Ph

Ph

Ph

Ph

Ph

Ph

2PF6ndash BAr f

ndash

Time (h)

Conversion ()

ee ()

10 94 90

7 98 97

Time (h)

Conversion ()

ee ()

4 gt99 86

4 gt99 94

L L L

1 Kauffman G B Coord Chem Rev 1974 12 105-149

2 Werner A Chem Ber 1911 44 1887-1898 and 1912 45 121-130

3 Ganzmann C Gladysz J A Chem Eur J 2008 14 5397-5400

4 Ghosh S K Ojeda A S Guerrero-Leal J Bhuvanesh N Gladysz J A Inorg Chem 2013

52 9369-9378

5 Thomas C Gladysz J A ACS Catalysis 2014 5 1134-1138

19

PL10

COMPLEXITY IN SIMPLICITY THE PROTOTYPE REACTIONS OF

CARBENE ANALOGS

MP Egorov

Zelinsky Institute of Organic Chemistry Russian Academy of Sciences Leninsky Prospect 47

Moscow 119991 Russia

20

PL11

SELECTIVELY ALKYLATED AND ARYLATED N-HETEROAROMATICS

VIA ACCEPTORLESS DEHYDROGENATIVE CONDENSATION

(ADC) REACTIONS

R Kempe

Lehrstuhl Anorganische Chemie II (Catalyst Design)University of Bayreuth Bavaria Germany

Dwindling reserves of crude oil and the resulting price increase of this and other fossil carbon

sources combined with environmental concerns have resulted in a call for the use of alternative

preferably renewable resources Aside from fuel ultimately a wide variety of chemical feedstocks

are derived from fossil sources Renewable lignocellulosic materials are indigestible and therefore

not useful as food products and can be processed to give alcohols and polyols These rather highly

oxidized hydrocarbons differ drastically in their chemical nature from the cracking products of

crude oil Thus there is a high demand for new reactions that utilize alcohols and convert them into

key chemicals Recently our group developed a sustainable catalytic pyrrole synthesis[1]

Secondary alcohols and amino alcohols are deoxygenated and linked selectively via the formation

of CndashN and CndashC bonds Two equivalents of hydrogen gas and two equivalents of water are

eliminated in the course of the reaction (Acceptorless Dehydrogenative Condensation ADC)

Alcohols based entirely on renewable resources can be used as starting materials The catalytic

synthesis protocol tolerates a large variety of functional groups which includes olefins chlorides

bromides organometallic moieties amines and hydroxyl groups Furthermore we have developed a

catalyst that operates efficiently under mild conditions This methodology could also be used to

synthesize selectively functionalized pyridines from alcohols[2] In the talk the development of

alcohol re-functionalization reactions and the design of catalyst systems that mediate these reactions

are discussed

[1] S Michlik R Kempe Nature Chem 2013 5 140

[2] S Michlik R Kempe Angew Chem Int Ed 2013 52 6450

21

PL12

THE CATALYST TODAY BIG BANG AND LIFE AFTER

IP Beletskaya

Lomonosov Moscow State University Department of Chemistry Moscow Russia

Nanocatalysis and catalysis by Lewis and Broensted acids will be considered in the lecture

22

Invited Lectures

23

24

IL1

CYCLIZATIONS OF ALKYNES FROM STEREOELECTRONICS TO

CASCADE TRANSFORMATIONS

IV Alabugin

Department of Chemistry and Biochemistry Florida State University Tallahassee Fl

One of the simplest organic functional groups the alkyne moiety is also one a useful starting point

for the design of cascade transformations which proceed through the formation of multiple C-C C-

H C-N and C-O bonds [1] In this talk I will illustrate how the revised stereoelectronic rules for

alkyne cyclizations [2] can be used for the bottom-up preparation of carbon nanostructures for

molecular electronics (ie graphene nanoribbons) In our approach alkyne chains of varying sizes

shapes and functionalities are built in a modular fashion and ldquozippedrdquo up into graphene

substructures via controlled cascades of all-exo or all-endo cyclizations [3]

Even in the presence of multiple functionalities alkyne cascades can be made chemoselective via

kinetic self-sorting of the pool of equilibrating radicals [4] Further synthetic opportunities are

presented by fusion of cyclization cascades with self-terminating fragmentations that allow use of

alkenes as synthetic equivalents of alkynes [5]

[1] Alabugin I V Gold B J Org Chem 2013 78 7777

[2] Alabugin I V Gilmore K Manoharan M J Am Chem Soc 2011 133 12608 Alabugin I

V Gilmore K Chem Commun 2013 49 11246

[3] Byers P M Rashid J I Mohamed R K Alabugin I V Org Lett 2012 14 6032 Byers

P J Am Chem Soc 2012 134 9609

[4] Mondal S Mohamed R K Manoharan M Phan H Alabugin I V Org Lett 2013 15

5650

[5] Mondal S Gold B Mohamed R K Alabugin I V Chemistry ndash Eur Journal 2014 in

print

25

IL2

ARTIFICIAL PHOTOSYNTHESIS USING TRANSITION METAL

COMPLEXES

O Ishitani

Department of Chemistry Tokyo Institute of Technology Japan

Both the problems of the global warming and shortage of the fossil fuels have brought about great

interest in photochemical utilization of CO2 with solar energy Efficient photocatalysts for CO2

reduction must be necessary for development of such an important technology

We have developed novel types of photocatalytic systems using metal complexes andor

semiconductors as a photocatalyst1 In this presentation I will focus on the architecture of two

types of the photocatalysts using transition metal complexes

(1) A mixed photocatalytic system including a ring-shaped Re(I) multinuclear complex as a

photosensitizer2

(2) Ru(II)-Re(I) and Ru(II)-Re(I) supramolecular photocatalysts3

The efficiency of the former photocatalytic system has been highest in the reported CO2-reduction

photocatalysts ( = 82) and the latter photocatalysts have been most robust (TON gt 3000)

References

1 (a) Yui T Tamaki Y Sekizawa K Ishitani O Photocatalytic reduction of CO2 from

molecules to semiconductors Top Curr Chem 2011 303 151-84 (b) Sekizawa K Maeda K

Domen K Koike K Ishitani O J Am Chem Soc 2013 135 4596

2 Morimoto T Nishiura C Tanaka M Rohacova J Nakagawa Y Funada Y Koike K

Yamamoto Y Shishido S Kojima T Saeki T Ozeki T Ishitani O J Am Chem Soc

2013 135 13266

3 (a) Gholamkhass B Mametsuka H Koike K Tanabe T Furue M Ishitani O Inorg

Chem 2005 44 2326 (b) Sato S Koike K Inoue H Ishitani O Photochem Photobiol Sci

2007 6 454 (c) Koike K Naito S Sato S Tamaki Y Ishitani O J Photochem Photobiol

A Chem 2009 207 109 (d) Tamaki Y Watanabe K Koike K Inoue H Morimoto T

Ishitani O Faraday Discuss 2012 155 115 (e) Tamaki Y Morimoto T Koike K Ishitani

O Proc Natl Acad Sci USA 2012 109 15673 (f) Tamaki Y Koike K Morimoto T

Ishitani O J Cat 2013 135 22 (g) Tamaki Y Koike K Morimoto T Yamazaki Y

Ishitani O Inorg Chem 2013 52 11902

26

IL3

A PARADIGM FOR THE PRACTICAL AND ECONOMICAL FORMATION

OF CARBONmdashCARBON AND CARBONmdashHETEROATOM BONDS

ORGANOCATALYTIC REDOX COUPLED TRANSITION METAL

CATALYZED DEHYDRATIVE BOND CONSTRUCTIONS

LS Liebeskind MG Lindale

Emory University Department of Chemistry Atlanta Georgia USA

The current world-wide focus on C-H functionalization is driven in part by the conceptual promise

of atom-efficient sustainable syntheses from readily available feedstocks Of equal conceptual

value is the dehydrative formation of CmdashC CmdashN and CmdashO bonds from common bioavailable

hydroxylic reactants like carboxylic acids alcohols and phenols Given the sustainable generation

of hydroxylic feedstocks dehydrative bond formations can impact all levels of synthesis

(commodities fine chemicals biologicals) if they are efficient economical practical and substrate

general And they are uniquely poised to contribute to the search for the sustainable conversion of

biomass to biofuels This lecture describes a paradigm for the conversion of hydroxylic reactants to

value-added CmdashC CmdashN and CmdashO products based on a practical organocatalytic redox-coupled

transition metal catalyzed dehydrative bond forming process

27

IL4

CHEMICAL SYNTHESIS USING AMPHOTERIC MOLECULES

AK Yudin

University of Toronto

Over the past seven years my lab has been exploring the use of amphoteric molecules in chemical

synthesis What started as a curiosity-driven project has turned into a sustained exploration of a

virtually untouched segment of chemistry characterized by molecules with unusual combinations of

functional groups The multifunctional nature arising from forced orthogonality enables amphoteric

molecules to participate in reactions of high atom- and step- economy thereby enabling efficient

syntheses characterized by minimal reliance on protecting groups

In this lecture I will illuminate several classes of reagents developed in our lab I will discuss the

discovery of bench-stable aldehydes equipped with a C-B bond at the alpha position These

intriguing molecules have enabled the synthesis of a rich palette of other reagents that contain

carbon-boron bonds at strategic positions With the growing repertoire of boron-containing

amphoteric molecules we are in a good position to explore ideas that range from reaction discovery

to the synthesis of boron-based biologically active compounds

I will also present the evolution of peptide macrocyclization technology driven by amphoteric

aziridine aldehydes As part of this study we are attempting to understand the conformational

preferences of peptide macrocycles As a result we are moving closer to our ultimate goal of

rationalizing the behavior of a wide range of substrate classes in our cyclization reactions as well as

understanding cellular activity of macrocycles I will conclude my talk with a discussion of our

integrative macrocyclization approaches and will present recent results of our protein crystallization

efforts

28

IL5

EMERGENT FUNCTION FROM COMPLEX ADAPTIVE CATALYSTS

VV Fokin

The Scripps Research Institute Department of Chemistry La Jolla California USA and Moscow

Institute of Physics and Technology Dolgoprudny Russia

Exploiting the versatility of catalytic processes requires rigorous interrogation of the constantly

changing environment of the catalyst Detailed understanding of critical events affecting a catalyst

such as activation and deactivation unproductive off-cycle pathways and changes in the nature of

dominant species are of critical importance The seemingly formidable challenge of controlling the

reactivity of complex catalytic systems that involve dynamic and rapidly equilibrating mixtures of

intermediates may in fact be their advantage well-defined (ie non-adaptable) catalysts are often

inefficient when compatibility with many functional groups and conditions is the goal

Examples of investigation of such catalytic reactions will be illustrated by case studies of transition

metal-catalyzed transformations of alkynes Alkynes are among the most energetic hydrocarbons

and transition metals enable selective and controlled manipulation of the triple bond revealing their

unique reactivity transformations of alkynes into heterocycles and into a variety of molecules with

new carbonndashheteroatom bonds These seemingly simple transformations involve an impressive

variety of intermediates yet proceed with high selectivity and efficiency maintaining their reactivity

in most complex environments such as the biological milieu of living organisms

29

IL6

RAPID PHOTOASSISTED ACCESS TO sp3-RICH POLYHETEROCYCLIC

SCAFFOLDS

OA Mukhina NNB Kumar WC Cronk WJ Umstead AG Kutateladze

Department of Chemistry and Biochemistry University of Denver USA

Photochemical reactions hold unparalleled promise for building prohibitively strained carbo‐ and

heterocyclic scaffolds which offer expeditious access to difficult synthetic targets not accessible via

ground state chemistry Yet photochemistry is underutilized by the synthetic community which is

especially true for Diversity Oriented Synthesis (DOS) In this context we have been developing a

new photoassisted synthetic methodology which will enhance synthetic chemistry toolbox and will

be compatible with DOS1 This new photoassisted synthetic methodology allows for rapid access

to topologically diverse polycyclic scaffolds decorated by various functional groups and

carboheterocyclic pendants rigidly or semi-rigidly held in a unique spatial configuration by these

novel core frameworks Access to such topologically diverse scaffolds is realized via key

photochemical steps and their combination with ground state reactions most prominently via the

recently discovered intramolecular cycloaddition reactions of azaxylylenes and quinomethanes

photogenerated via excited state intramolecular proton transfer Details of an experimental and

theoretical mechanistic study to gain deeper understanding of underlying processes in the excited

states will also be discussed

A typical example of rapid growth of complexity in a photoassisted synthesis of enantiopure

conformationally locked ribofuranosylamines spiro-linked to oxazolidino-diketopiperazines via a

straightforward ldquoassemblyrdquo of a threonine-based photoprecursor photochemical transformation

and a simple post-photochemical modification is shown below

[1] (a) Mukhina OA Kumar NNB Arisco TM Valiulin RA Metzel GA Kutateladze

AG Angew Chem Int Ed 2011 50 9423-9428 (b) Nandurkar NS Kumar NNB

Mukhina OA Kutateladze AG ACS Combinatorial Sci 2013 15 73-76 (c) Kumar

NNB Mukhina OA Kutateladze AG J Am Chem Soc 2013 135 9608-9611 (d)

Cronk WC Mukhina OA Kutateladze AG J Org Chem 2014 791235-1246

30

IL7

TRANSITION METAL CLUSTERS UNAVOIDABLE CONTAMINANTS OR

IMPORTANT PLAYERS IN SOLUTION

VP Ananikov

Zelinsky Institute of Organic Chemistry Russian Academy of Sciences Leninsky Prospect 47

Moscow 119991 Russia Department of Chemistry Saint Petersburg State University Stary

Petergof 198504 Russia

Application of transition metal catalysis in organic synthesis is an area of outstanding progress with

prominent achievements in carbon-carbon cross-coupling carbon-heteroatom bond formation and

atom-economic construction of organic molecules

Mechanistic studies have revealed two different frameworks for catalytic processes in solution

depending on the nature of selected system and on the type of catalyst precursor used single type

metal species catalysis or multiple metal species catalysis [1] The first type of systems is widely

utilized and it is based on well-defined metal complex with strongly bound ligands The catalyst

precursor undergoes only partial or minor chemical modifications prior entering the catalytic cycle

In this model the formation of other metal derivatives is not facilitated and the active core of the

catalyst is preserved throughout the catalytic cycle

The second model can be considered as multiple metal species catalysis (in some cases - ldquococktailrdquo

of catalysts) and involves a range of simultaneously present and dynamically interchangeable metal-

containing species such as metal complexes clusters and nanoparticles [2] Such mechanistic

picture may be expected when in situ generated catalysts are employed or upon usage of

nanoparticles as catalysts precursors

It is of much interest to reveal the role of metal clusters in these catalytic systems Formation of

clusters was detected in many cases although their role remains unclear In some cases the presence

of clusters was related to decomposition of the active form while in the other cases the formation of

dinuclear and polynuclear species is an important stage of catalyst evolution in solution

We have investigated soluble metal complexes and nanoparticles of Pd Ni Pt and Au for

development of efficient catalytic systems for selective carbon-heteroatom and carbon-carbon bond

formation in solution [3-5] Homogeneous transition-metal-catalyzed reactions and heterogeneous

nanoparticle-catalyzed reactions were considered with a focus on metal species interconversions

and nanoparticle contamination of homogeneous catalytic systems

References

[1] Kashin AS Ananikov V P J Org Chem 2013 78 11117 (doi 101021jo402038p)

[2] Ananikov V P Beletskaya I P Organometallics 2012 31 1595 (doi 101021om201120n)

[3] Zalesskiy S S Sedykh A E Kashin A S Ananikov V P J Am Chem Soc 2013 135

3550 (doi 101021ja311258e)

[4] Ananikov V P Orlov N V Zalesskiy S S Beletskaya I P Khrustalev V N Morokuma

K Musaev D G J Am Chem Soc 2012 134 6637 (doi 101021ja210596w)

[5] Kashin A S Ananikov V P Top Catal 2013 56 1246 (doi 101007s11244-013-0091-5)

31

IL8

SIMPLE COPPER CATALYSTS FOR C-C C-N AND C-O BONDS

FORMATION

F Monnier

Institut Charles Gerhardt (UMR 5253) ENSCM FRANCE

Since its renaissance in 2001 [1] the copper cross-coupling of nucleophiles with aryl halides has

been increasingly studied [2] In this account we exposed our last contribution for the formation of

C-C [3] C-N [4] and C-O [5] bonds catalyzed by a cheap and simple combination of copper salts

and -diketone ligands

1 a) M Taillefer H-J Cristau P P Cellier J-FSpindler Env SAU2001-1009 and SAU2001-

01044 patents Fr2833947-WO0353225 (Pr Nb Fr 2001 16547) M Taillefer H-J Cristau P

P Cellier J-F Spindler A Ouali Fr2840303-WO03101966 (Pr Nb Fr 2002 06717) b) S L

Buchwald A Klapars J C Antilla G E Job M Wolter F Y Kwong G Nordmann E J

HennessyWO02085838 (priority number US0286268 2001)

2 For a review see F Monnier M Taillefer Angew Chem Int Ed 2009 48 6954-697

3 a) G Danoun A Tlili F Monnier M Taillefer Angew Chem Int Ed 2012 51 12815 b)

MTaillefer F Monnier A Tlili G Danoun PCT Int Appl (2013) WO 2013 EP61697

20130606 FR20120055275 20120606

4 a) A Tlili F Monnier M Taillefer Chem Commun 2012 48 6408-6410 b) E Racine F

Monnier J-P Vors M Taillefer Chem Commun 2013 49 7412 c) E Racine F Monnier J-

P Vors M Taillefer Org Lett 2011 13 2818

5 a) A Tlili N Xia F Monnier M Taillefer Angew Chem Int Ed 2009 48 8725-8728

32

IL9

INTERACTIONS IN IONIC LIQUIDS PROBED BY NMR SPECTROSCOPY

DISTANCES CONFORMATIONS AND MORE

R Giernoth A Broehl Y Lingscheid

University of Cologne Department of Chemistry Koeln Germany

One often-mentioned aspect of ionic liquids (ILs) is that they are ldquodesigner solventsldquo whose

properties can be designed for any particular need [1] Obviously it is impossible to choose a

different property for a given IL but only a different IL entirely To be able to sensibly do so it is

necessary to know about the supramolecular structures and the governing interactions in the ionic

liquid phase

NMR spectroscopy and the nuclear overhauser effect

spectroscopy (NOE) in particular is the method of choice

for the investigation of ion pair interactions [2] The

NOE arises due to inter- and intramolecular cross

relaxation

To be able to precisely measure interactions in solution

an internal distance standard is needed We have

synthesized a monofluorinated ionic liquid which was subsequently employed in NOE-based NMR

investigations for the determination of distances and interactions in the ionic liquid phase

In a different project we are studying the influence of

different ionic liquids on peptide conformations much

in accord with the well-known Hofmeister series of ions

[3] With the help of a model system we are going to

demonstrate that the choice of ions has a strong effect on

the tertiary structure of different peptides in solution

and how these effects can be used for new non-native

peptide chemistry

References

[1] for reviews see JP Hallett T Welton Chem Rev 2011 111 3508-3576 E J Maginn J

Phys Condens Matter 2009 21 1ndash17

[2] P S Pregosin Pure Appl Chem 2009 81(4) 615ndash633 Y Lingscheid S Arenz R Giernoth

ChemPhysChem 2012 13 261ndash266

[3] F Hofmeister Arch Exp Pathol Pharmakol 1888 64 247

33

IL10

APPLICATION OF α-CF3-SUBSTITUTED DIAZOCOMPOUNDS IN

ORGANIC SYNTHESIS AND CATALYSIS

SN Osipov DV Vorobyeva IE Tsishchuk

AN Nesmeyanov Institute of Organoelement Compounds Russian Academy of Sciences Moscow

An efficient pathway to multifunctional CF3-containing aromatic heteroaromatic and heterocyclic

compounds including cyclic amino carboxylic and amino phosphonic acid derivatives have been

developed The method is based on in situ generation of highly electrophilic CF3-carbene species

from the corresponding α-diazo carboxylates or phosphonates under Cu- or Rh-catalysis and their

reactions with appropriate nucleophilic partners1-4

The further applications of the reaction products in metal-catalysed transformations of different

types eg such as ring closing diene and ene-yne metathesis intramolecular Pauson-Khand

reaction as well as [2+2]-cycloaddition open an access to new families of fluorinated molecules

References

1 DV Vorobyeva AK Mailyan AS Peregudov NM Karimova TP Vasilyeva IS

Bushmarinov C Bruneau PH Dixneuf SN Osipov Tetrahedron 2011 67 3524

2 AK Mailyan IM Krylov C Bruneau PH Dixneuf SN Osipov Synlett 2011 2321

3 AK Mailyan IM Krylov C Bruneau PH Dixneuf SN Osipov Eur J Org Chem

2013 5353

4 IE Tsishchuk DV Vorobyeva AS Peregudov SN Osipov Eur J Org Chem 2014

2480

34

IL11

NEW ADVANCES IN ORGANOMETALLIC AND PHOSPHORUS

ELECTROCHEMISTRY

DG Yakhvarov OG Sinyashin

AEArbuzov Institute of Organic and Physical Chemistry Laboratory of Organometallic and

Coordination Compounds Kazan Russian Federation

The development of modern chemical science and creation of new industrially applicable

technologies are focused on application of effective and ecologically safe methods for the

preparation of important and useful chemical compounds and materials The combination of

transition-metal catalysis and organic electrosynthesis has attracted increasing attention due to the

high selectivity and efficiency of this approach in the synthetic preparation of various compounds

bearing carbon-carbon and carbon-element bonds The mild conditions single-stage process cyclic

regeneration of the catalyst and convenient and relatively inexpensive form of the energy used are

the main advantages of electrochemical methods Application of electrochemical processes to large-

scale production (macroscale synthesis) has led to significant development of the chemical

technologies of the 21st century due to easy access to highly reactive intermediates and tuning of

the reactivity of the substrate used during the synthetic process by simple adjustment of the

electrode potential

The elaborated in our research group electrochemical methods have been successfully applied for

generation of organometallic sigma-complexes1 which are important intermediates of different

carbon-carbon and carbon-element coupling processes selective preparation of organophosphorus

compounds from white phosphorus2 activation of inert oligophosphorus moieties formed in the

coordination sphere of transition metal complexes3 selective cleavage of the tungsten-phosphorus

bond resulting in valuable metal-free phosphorus heterocycles obtained via phosphinidene

intermediates4

Herein we present recent advances in synthetic application of the electrochemical techniques for

preparation and activation of organonickel complexes1 and generation of new previously known as

unstable phosphorus intermediates5 which can be applied for preparation of practically useful

organophosphorus compounds transition metal catalysts and magnetically active materials6

Acknowledgements Financial support from the Russian Scientific Fund (project 14-13-01122) and

Russian Foundation for Basic Research (project 09-03-00933-a) is gratefully acknowledged

References

[1] DGYakhvarov AFKhusnuriyalova OGSinyashin Organometallics 2014 in press

[2] DGYakhvarov EVGorbachuk OGSinyashin Eur JInorgChem 2013 4709

[3] DYakhvarov PBarbaro LGonsalvi SMantildeas SMidollini AOrlandini MPeruzzini

OSinyashin FZanobini Angew Chem Int Ed 2006 45 4182

[4] DGYakhvarov YuHBudnikova NHTran Huy LRicard FMathey Organometallics

2004 23 1961

[5] DYakhvarov MCaporali LGonsalvi ShLatypov VMirabello IRizvanov OSinyashin

PStoppioni MPeruzzini Angew ChemIntEd 2011 50 5370

[6] DYakhvarov ETrofimova OSinyashin OKataeva PLoumlnnecke EHey-Hawkins APetr

YuKrupskaya VKataev RKlingeler BBuumlchner Inorg Chem 2011 50 4553

35

IL12

TRIFLUOROMETHYLATION BY SUNLIGHT-PROMOTED

PHOTOREDOX CATALYSIS

T Koike M Akita

Tokyo Institute of Technology Chemical Resources Laboratory Yokohama Japan

Photoredox catalysis 1 mediated by photo-sensitizers (eg [Ru(bipy)3]

2+ and relevant Ir complexes)

has attracted increasing attention as practical green synthetic chemical processes because they are

visible light-promoted redox-neutral reactions

We have demonstrated that photoredox catalysis is a powerful synthetic tool in particular for

trifluoromethylation of olefinic substrates which is the topic of the presentation23

In all cases

electron transfer from the photoexcited metal species to an electrophilic CF3-reagent generates the

key CF3 radical intermediate together with the cationic species of the catalyst Subsequent

addition of the CF3 radical to the olefinic substrate followed by oxidation of the resultant carbon

radical intermediate by the cationic metal species gives the carbocationic intermediate which is

trapped by nucleophiles or deprotonated to furnish the coupling products The sequential redox

processes make the system redox-neutral It is remarkable that the reactions are promoted not only

by artificial light sources (eg Xe lamp and blue LED lamps) but also by sunlight

References 1) C K Prier D A Rankic and D W C MacMillan Chem Rev 113 5322 (2013)

2) T Koike and M Akita (a) Synlett 24 2492 (2013) (b) Topics in Cat 259 in press (2014)

(DOI 101007s11244-014-0259-7) 3) Y Yasu T Koike M Akita et al (a) Angew Chem Int

Ed 51 9567 (2012) (b) Chem Commun 49 2037 (2013) (c) Org Lett 15 2136 (2013) (d)

Org Lett 16 in press (2014) (DOI 101021ol403500y) (e) Beilstein J Org Chem submitted

(f) to be submitted see also (g) Chem Commun 48 5355 (2012) (h) ibid 49 7249 (2013)

36

IL13

CYCLIC HYPERVALENT IODINE REAGENTS A TREASURE OF

REACTIVITY FOR CATALYSIS AND SYNTHESIS

J Waser

Ecole Polytechnique Federale de Lausanne ISIC SB LCSO Lausanne Switzerland

The non-classical four electrons three centers bonds of hypervalent iodine are weaker than normal

classical bonds This confers an exceptional reactivity to these compounds as oxidants or atom-

transfer reagents Cyclic hypervalent iodine reagents are especially interesting as they combine

enhanced stability with unique opportunities for reactivity modulation In particular our group has

been interested in the development of alkynylation methods using cyclic EthynylBenziodoXolone

(EBX) hypervalent iodine reagents1 Interesting recent results of our research in the area includes

the first example of gold-catalyzed domino cyclization-alkynylation2 and a highly efficient and

practical alkynylation method for thiols3 Herein we will present our most recent work in the area

of electrophilic alkynylation as well as the extension of the use of cyclic hypervalent iodine

reagents to other functionalization reactions

References

1 JP Brand J Waser Chem Soc Rev 2012 41 4165-4179

2 Y Li J P Brand J Waser Angew Chem Int Ed 2013 52 6743-6747

3 R Frei J Waser J Am Chem Soc 2013 135 9620-9623

37

IL14

THEORY AND COMPUTATION PROVIDE INSIGHTS AND DISCOVERY

ON CHEMICAL REACTIONS OF COMPLEX MOLECULAR SYSTEMS

K Morokuma12

1 - Fukui Institute for Fundamental Chemistry Kyoto University Kyoto Japan

2 - Cherry L Emerson Center for Scientific Computation and Department of Chemistry Emory

University Atlanta GA USA

The chemical reaction that creates destroys reorganizes chemical bonds to produce new

compounds is the most important subject of chemistry Theoreticalcomputational studies have

come a long way and are now playing the central role in providing insights in understanding the

mechanism and dynamics of chemical reactions as well as in discovery of new reaction mechanisms

and reaction systems The theory can study not only the reaction of the ground state of molecules in

gas phase but also reactions of excited electronic states as well complicated reactions of complex

molecular systems The information theoreticalcomputational studies can provide is often

complementary to the information experimental studies provide and research on chemical reactions

is becoming impossible without strong collaboration between theorists and experimentalists

In the present talk I will discuss some of our recent studies of chemical reactions We have

developed the Global Reaction Route Mapping (GRRM) strategy for automatic exploration of

reaction pathways of complex molecular systems The ADDF (anharmonic downward distortion

following) and the AFIR (artificial force induced reaction) methods in the GRRM strategy have

been used for determination of not only energy minima and saddle points on the potential energy

hypersurfaces but also minima and saddle points on the conical intersection and crossing seam

hypersurfaces I will discuss the GRRM strategy and applications to several reaction systems

including photodissociation reactions catalytic reactions and enzymatic reactions

38

IL15

COMPUTATIONAL INSIGHTS INTO C-H FUNCTIONALIZATION

JUNGLE

D Musaev

Cherry L Emerson Center for Scientific Computation Emory University Atlanta Georgia USA

I will present our integrated and

collaborative approaches to the

Transition metal catalyzed C-H bond

functionalization I will elaborate our

efforts on understanding the transition

metal catalyzed C-H bond alkylation

and amination reactions and analyze

the factors controlling the reactivity of

these reactions and make intriguing

predictions I will discuss our latest

results [1] on the mono-protected amino acid ligands (MPAA) promoted Pd(II)-catalyzed

enantioselective CndashH activation reactions The presented computation allowed us to gain insights

into the mechanisms nature of active species a ligand coordination mode to the Pd(II) and

transition state structure of the CndashH activation step Our findings were supported by experiments

[1] D G Musaev T M Figg and A L Kaledin Chem Soc Rev DOI 101039C3CS60447K

(2014)

PR3

Ar

Pd

I

Ph

CsF

HCsPd

RZ ZR

Pd

ZRZR

ZR

Pd

ZR

Pd

RZ ZR

Pd

ZR

ZR

ZR ZRPd

Active

Inactive

Cs2-I-F assisted

PdNO

N

O

PG

H Ph

H

i-Pr

H

O

-

O

Ligand accelerated

Protecting Group effectBase (Cs)-effectPd-cluster effect

C-H FUNCTIONALIZATION

DIRECT Ar-Ar COUPLING

SELECTIVE RSHRSeH + C C

Pd(II)- PRECATALYST

39

IL16

A NOVEL TRIFLUOROMETHANESULFONYL HYPERVALENT

IODONIUM YLIDE FOR TRIFLUOROMETHYLTHIOLATION

N Shibata

Nagoya Institute of Technology Department of Nanopharmaceutical Sciences Nagoya Japan

In the last few decades numerous methods for the introduction of a trifluoromethylthio group into

organic compounds have been developed The main strategies are indirect methods including

halogen-fluorine exchange and trifluoromethylation of sulfur-containing compounds such as

disulfides thiols and thiolates Obviously the most attractive and ideal route to constitute the CF3S

moiety is the direct introduction of this functional group However in this approach some

limitations are usually encountered including the use of gaseous and highly toxic reagents such as

CF3SCl or unstable reagents and the modest scope of substrates Although several transition

metal-mediated or catalyzed trifluoromethylthiolation methods have been developed the substrates

are mostly limited to aromatic compounds Recently Billard and co-workers reported that

trifluoromethanesulfanylamides were effective for trifluoromethylthiolation of alkenes alkynes

indoles and organometallic species More recently Lu and Shen also developed a novel hypervalent

iodine reagent for the trifuoromethylthiolation of aryl and vinyl boronic derivatives alkynes and β-

ketoesters Even though these direct trifluoromethylthiolation reagents are shelf-stable a more

critical issue is the fact that these CF3S regents should be prepared in advance by

trifluoromethylthiolations or related trifluoromethylations Due to these limitations and negative

aspects it is thus still necessary to develop an efficient and easily available reagent to introduce the

CF3S moiety directly In contrast to the CF3S unit a trifluoromethanesulfonyl (CF3SO2) unit is

stable and often found in commonly used organic reagents such as CF3SO2Cl CF3SO2Na CF3SO2H

and (CF3SO2)2 In this context we came up with a novel idea of using ubiquitous CF3SO2

compounds as reagents for introducing the CF3S unit under reductive conditions As a part of our

recent work on the chemistry of trifluoromethanesulfonyl compounds (triflones) we herein disclose

a novel trifluoromethanesulfonyl hypervalent iodonium ylide as a shelf-stable reagent for

electrophilic-type trifluoromethylthiolation A wide variety of nucleophiles are nicely converted

into the corresponding trifluoromethylsulfanyl products by this reagent

Reference Y-D Yang A Azuma E Tokunaga M Yamasaki M Shiro N Shibata J Am

Chem Soc 135 8782 (2013)

40

IL17

CATALYSIS-ASSISTED SIGNAL ENHANCEMENT IN NUCLEAR

MAGNETIC RESONANCE

IV Koptyug

International Tomography Center SB RAS Novosibirsk Russia

When parahydrogen (nuclear spin isomer of H2) is used in catalytic hydrogenations instead of

normal H2 the NMR signals of reaction products and intermediates can be enhanced by 3-4 orders

of magnitude and more owing to the phenomenon of parahydrogen-induced polarization (PHIP)

This possibility has been explored previously in the context of activation of H2 by transition metal

complexes and clusters in solution It has been shown that PHIP can help to detect reaction products

and short-lived intermediates not detectable by conventional NMR As most of the industrial

catalytic processes are heterogeneous it would be desirable to employ PHIP in the NMR studies of

heterogeneous catalysts and catalytic reactions The objective of our research is thus to extend the

scope of PHIP applications to the heterogeneously (HET) catalyzed hydrogenation reactions and to

develop a hypersensitive NMR-based technique for the in situ and operando studies of

heterogeneous catalytic processes In addition HET-PHIP can be employed to produce catalyst-free

hyperpolarized liquids and gases for novel MRI applications including the advanced in vivo studies

We demonstrate that similar to their homogeneous counterparts heterogenized transition metal

complexes are able to produce strong NMR signal enhancements when parahydrogen is used in the

hydrogenation reactions [1] Our recent results show that various immobilized metal complexes are

can produce HET-PHIP both in liquid phase and in gas phase hydrogenations In contrast for

supported metal catalysts (eg PtAl2O3) dissociative hydrogen chemisorption and rapid migration

of H atoms on the metal surface were expected to make the required pairwise hydrogen addition to

a substrate molecule impossible Nevertheless we have shown that PHIP can be successfully

observed both in liquid-solid and in gas-solid heterogeneous hydrogenations catalyzed by supported

metal catalysts [1] The NMR signal enhancement was found to be sensitive to the metal

nanoparticle size and shape the nature of the metal and support and the type of substrate used in

the reaction Recently HET-PHIP effects were also demonstrated for several metal oxides and bulk

unsupported metals used as hydrogenation catalysts [2] The implications of these results for the

mechanisms of heterogeneous hydrogenation processes are discussed [13] Further potential

extensions of the technique will be presented including the use of metal-free catalysts for activating

parahydrogen [4] and the prospects of using nuclear spin isomers of molecules other than H2 to

further extend the range of reactions and processes that can be explored in detail using the PHIP

technique [5] In addition to applying HET-PHIP to the mechanistic and kinetic studies of

heterogeneous hydrogenations several MRI applications of HET-PHIP have been already

demonstrated including MR imaging of a catalytic reaction in an operating model microreactor [6]

1 KV Kovtunov VV Zhivonitko IV Skovpin DA Barskiy IV Koptyug Top Curr Chem 338 123

(2013)

2 KV Kovtunov DA Barskiy OG Salnikov AK Khudorozhkov VI Bukhtiyarov IP Prosvirin IV

Koptyug Chem Commun 50 875 (2014)

3 OG Salnikov KV Kovtunov DA Barskiy AK Khudorozhkov EA Inozemtseva IP Prosvirin VI

Bukhtiyarov IV Koptyug ACS Catal 4 2022 (2014)

4 VV Zhivonitko V-V Telkki K Chernichenko TJ Repo M Leskela V Sumerin IV Koptyug J

Amer Chem Soc 136 598 (2014)

5 VV Zhivonitko KV Kovtunov PL Chapovsky IV Koptyug Angew Chem Int Ed 52 13251

(2013)

6 VV Zhivonitko V-V Telkki IV Koptyug Angew Chem Int Ed 51 8054 (2012)

41

IL18

-BOND ACTIVATION REACTION BY TRANSITION METAL AND MAIN-

GROUP ELEMENT COMPOUNDS AND CATALYTIC REACTION

INCLUDING IT

S Sakaki

Fukui Institute for Fundamental Chemistry Kyoto University Takano Sakyo-ku Kyoto 606-8103

Japan

The -bond activation by transition metal complexes attracts a lot of interests in theoretical and

organometallic chemistries because it is crucial in many catalytic reactions by transition metal

complexes In our understanding -bond activation is classified to two categories the concerted

oxidative addition to M (metal) the stepwise oxidative addition via nucleophilic attack the

oxidative addition to M-L (L = neutral ligand) and the heterolytic activation by M-X (X = anionic

ligand) activation by metal center only and that by the metal-ligand moiety12

MLn + R1-R2 cis-MLn(R1)(R

2) (1)

MLn + R1-X [MLn(R1)] --(X) trans-MX(R

1)Ln (2)

MLLn + R1-R2 MLn(R1)(L-R

2) (3)

MXLn + R1-R2 MLn(R1) + R

2-X (4)

We theoretically investigated these reactions and elucidated the characteristic electronic processes

and clear understanding2 We also theoretically investigated catalytic reactions including -bond

activation In this talk we wish to present our recent theoretical studies of carboxylation of

phenylchloride catalysed by a nickel(0) complex hydrosilylation of carbon dioxide catalyzed by

germanium(II)- and zinc(II)-hydride compounds3

In my talk I wish to present comprehensive understanding of these -bond activation reactions and

the importance of -bond activation reaction in such catalytic reactions as CO2 conversion and

cross-coupling reactions

References

1 S Sakaki Y-y Ohnishi H Sato Chem Record 10 29 (2010) W Guan F B Saeed S

Sakaki Inorg Chem in press

2 N Ochi Y Nakao H Sato S Sakaki J Am Chem Soc 129 8615 (2007) N Ochi Y Nakao

H Sato S Sakaki J Phys Chem A 114 659 (2010)

3 N Takagi and S Sakaki J Am Chem Soc 135 8955 (2013) M Deschmukh to be submitted

42

IL19

NONPLANAR HETEROAROMATICS SYNTHESIS AND SELF-ASSEMBLY

M Stepien

Wydziaі Chemii Uniwersytet Wrocіawski

Even though π-electron aromaticity is typically associated with planar structures several classes of

distorted π-aromatics are known including a variety of twisted helical bowl-shaped or tubular

systems Such distortions are of fundamental interest because they provide a means of testing

different aspects of aromaticity theory but they also may have practical consequences as a

potential method of fine-tuning the electronic structure and self-assembly properties of aromatic

compounds

In this contribution two synthetic approaches to nonplanar heteroaromatics will be discussed One

is based on oxidative coupling reactions of pyrrole-containing precursors and is exemplified by our

recent syntheses of peripherally fused porphyrin derivatives1 (1 and 2) and bipyrroles

2 Compounds

1ndash2 are characterized by bathochromically shifted electronic absorptions and very high extinction

coefficients Phenanthroporphyrins 1 and their complexes reveal substitution-dependent aggregation

in solution and form columnar mesophases in the condensed phase The zinc(II) complex of

benzochrysenoporphyrin 2 was found to form a unique 3D-ordered mesophase containing discrete

multiporphyrin aggregates

The other approach to nonplanar aromatics explored in our laboratory which is suitable to the

synthesis of bowl- or belt-shaped structures involves the so-called fold-in synthesis3 performed on

appropriately designed macrocyclic precursors The fold-in concept can be realized using different

reactivity types including Ullmann-type reductive coupling as in the recent synthesis of

chrysaorole (3)34

and FriedelndashCrafts alkylation5

(1) Myśliwiec D Donnio B Chmielewski P J Heinrich B Stępień M J Am Chem Soc

2012 134 4822ndash4833

(2) Gońka E Myśliwiec D Lis T Chmielewski P J Stępień M J Org Chem 2013 78

1260ndash1265

(3) Stępień M Synlett 2013 24 1316ndash1321

(4) Myśliwiec D Stępień M Angew Chem Int Ed 2013 52 1713ndash1717

(5) Kondratowicz M Myśliwiec D Lis T Stępień M in preparation

43

IL20

RHODIUM N-HETEROCYCLIC CARBENE COMPLEXES AS EFFICIENT

CATALYSTS FOR X-H ADDITIONS TO ALKYNES THE QUEST FOR

SELECTIVITY

R Castarlenas A Di Giuseppe L Rubio-Perez L Palacios R Azpiroz V Polo JJ Perez-

Torrente LA Oro

ISQCH Universidad de Zaraaragoza-CSIC

The development of new catalytic systems for the synthesis of added-value products in a selective

manner and with high atom economy is nowadays an important task In this context our group has

recently prepared new rhodium complexes bearing an N-heterocyclic carbene (NHC) ligand that

have been disclosed to be very active and gem-selective for X-H additions across C-C triple

bonds1-4

Experimental and theoretical (DFT) mechanistic studies indicate that the presence of a

bulky powerful electron-releasing NHC and the rational choice of the auxiliary ligands is essential

in order to control the selectivity towards the formation of Markonikov-type products

1 A Di Giuseppe R Castarlenas JJ Perez-Torrente M Crucianelli V Polo R Sancho FJ

Lahoz LA Oro J Am Chem Soc 2012 134 8171

2 L Palacios MJ Artigas V Polo FJ Lahoz R Castarlenas JJ Perez-Torrente LA Oro ACS

Catal 2013 3 2910

3 L Rubio-Peacuterez R Azpiacuteroz A Di Giuseppe V Polo R Castarlenas JJ Perez-Torrente LA

Oro Chem Eur J 2013 19 15304

4 R Azpiacuteroz A Di Giuseppe R Castarlenas JJ Perez-Torrente LA Oro Chem Eur J 2013

19 3812

44

IL21

CATALYTIC OLEFINATION REACTION ndash UNIVERSAL METHOD FOR

SYNTHESIS OF ALKENES

VG Nenajdenko

Moscow State University Department of Chemistry Leninskie Gory Moscow 119992

Catalytic olefination reaction represents new approach to the preparation of double C=C bond N-

unsubstituted hydrazones can be converted into alkenes by treatment with polyhalogenated alkanes

in presence of a base and catalytic amounts of copper salts The reaction has a wide synthetic scope

allowing to prepare both alkyl and aryl halogenoalkenes including fluorinated ones and derivatives

with functional groups Simple experimental procedure which does not require using of

organometallic or toxic organophospourous compounds affordable price and availability of starting

materials high yields and stereoselectivity are distinct advantages of the reaction

R2

R1

COOR

Cl

R2

R1

Cl

CN

R2

R1

F

F

O

R2

R1

R2

R1

Cl

Cl

R2

R1

Br

Br

R2

R1

CH2OH

Cl

R2

R1

CClF2

F

R2

R1

CF3

Cl

R2

R1

Cl

F

R2

R1

CBrF2

F

CBrF2R

R2

R1

CBrF2

F

F

R2

R1

CONR2

Cl

R2

R1

Cl

O

O

R2

R1

I

H

R2

R1

Cl

H

R2

R1

Br

H

45

IL22

HOW TO MAKE COMPLEX MOLECULES FROM SIMPLE STARTING

MATERIAL THE PALLADIUM A POWERFUL TOOL

J Suffert

University of StrasbourgCNRS

In addition to molecular complexity the challenge of the chemist today is also the quest for

efficiency of the synthetic route and maximization of structural complexity Our laboratory

investigations focus for several years on the study of an unprecedented cascade reaction involving a

rare 4-exo-dig cyclocarbopalladation followed by a terminated cross-coupling with an

organometallic reagent A 6 - or 8 -electrocyclization can occur leading to new tricyclic structures

The seminar will show that we can offer an easy access to complex polycyclic molecules resulting

from readily available simple starting materials Eventually it will be possible to propose the

elaboration of a large collection of unprecedented structurally novel molecules based on recent

promising results Below are represented several complex structures that has been prepared through

the powerful 4-exo-dig cyclocarbopalladation Many other extension of this method have not been

so far explored and can afford a multitude of new and original scaffolds

46

IL23

SYNTHESIS OF TIN AND LEAD ANALOGS OF CYCLOPENTADIENYL

ANION AND THEIR APPLICATION TO TRANSITION-METAL

COMPLEXES

M Saito

Department of Chemistry Graduate School of Science and Engineering Saitama University

Shimo-okubo Sakura-ku Saitama-city Saitama 338-8570 Japan

We succeeded in the generation of tetraphenyldilithiostannole 1a[1]

and its considerable aromatic

character was established by X-ray diffraction analysis and theoretical calculations[2]

The lead

analog tetraphenyldilithioplumbole 2 was also found to be aromatic indicating that the concept of

aromaticity is expanded to lead-bearing carbon cycles[3]

After the synthesis of heavier congeners of Cp anion attention was next paid to the preparation of

transition-metal complexes with such heavier Cp ligands The first heavier metallocene was a

ruthenocene bearing a germole ligand[4]

and transition-metal complexes with silole and germole

ligands have already been synthesized The straightforward method for the synthesis of such

metallocenes is the reactions of metallole anions and dianions with transition-metal reagents

However the reactions using stannole anions and dianions had never been reported until recently

We examined the reaction of tetraphenyldilithiostannole 1b[5]

with [CpRuCl]4 and butterfly

complex 3 was obtained instead of an expected ruthenocene[6]

The reaction of 1b with Cp2TiCl2

afforded three-membered ring compound 4 with unique electronic states[7]

The synthesis of the first

neutral triple-decker complex 5 with group 14 metallole ligands was also achieved using silyl-

substituted dilithiostannole 1c

M

R2

R2

R1

R1

L i

L i

M = S n R1

= R2

= P h

M = S n R1

= R2

= E t

M = S n R1

= M e 3S i R2

= P h

M = P b R1

= R2

= P h

1 a

1b

1c

2

R u

R u

S n S n

E tE t

E t

E t

E t

E t

E t

E t

C p

C p

3

T i

S n

S nC p

C p

4

S n

S iM e 3

M e 3S i

P h

P h

R u C p C p R u

5

References

[1] Saito M Haga R Yoshioka M Chem Commun 2002 1002

[2] Saito M Haga R Yoshioka M Ishimura K Nagase S Angew Chem Int Ed 2005 44

6553

[3] Saito M Sakaguchi M Tajima T Ishimura K Nagase S Hada M Science 2010 328

339

[4] Freeman W P Tilley T D Rheingold A L Ostrander R L Angew Chem Int Ed Engl

1993 32 1744

[5] Saito M Kuwabara T Kambayashi C Yoshioka M Ishimura K Nagase S Chem Lett

2010 39 700

[6] Kuwabara T Saito M Guo J D Nagase S Inorg Chem 2013 52 3585

[7] Kuwabara T Guo J D Nagase S Saito M Angew Chem Int Ed 2014 53 434

47

IL24

NEW METHODS FOR PEROXIDE SYNTHESIS

AO Terentev

ZIOCh Moscow Russia

In the last decades organic peroxides have received considerable attention from chemists and drug

design experts which is associated with a need in the search for drugs for the treatment of parasitic

diseases such as malaria and helminth infections Considerable progress has been made in the

design of effective peroxide antimalarial drugs Some synthetic peroxides exhibit activity equal to

or higher than that of artemisinin Peroxides having antitumor or growth-regulatory activity were

also documented In our work we developed new methods for synthesis of various types of

peroxides

It was found that some peroxides posesses pronounced antischistosomal properties and anticancer

activity This work is supported by the Grant of the Russian Foundation for Basic Research (Grant

14-03-00237) and by the Program for Basic Research of the Presidium of the Russian Academy of

Sciences

References

[1] Terentev A Borisov D Yaremenko I Chernyshev V Nikishin G JOrgChem 75 5065-

5071 2010

[2] Terentev A Yaremenko I Chernyshev V Dembitsky V Nikishin G JOrgChem 77

1833-1842 2012

[3] Ingram K Yaremenko IA Krylov I Hofer L Terentev A O Keiser J JMedChem 55

(20) 8700ndash8711 2012

[4] Terentev A O Yaremenko I A Vil V A Dembitsky V M Nikishin G I Synthesis

246-250 2013

[5] Terentev A O Yaremenko I A Vil V A Моisееv I K Konrsquokov S A Dembitsky V

M Levitsky D O Nikishin G I Org Biomol Chem 11 2613ndash2623 2013

[6] IA Yaremenko AO Terentrsquoev VA Vilrsquo RA Novikov VV Chernyshev VA Tafeenko

DO Levitsky F Fleury GI Nikishin Chemistry - A European Journal DOI

101002chem201402594

48

IL25

SYNERGISM BETWEEN THEORY AND EXPERIMENTS IN

ASYMMETRIC CATALYSIS TRANSITION STATE MODELING FOR

RATIONALIZATIONS AND CATALYST DESIGN

RB Sunoj

Department of Chemistry Indian Institute of Technology Bombay Powai Mumbai 400076

Computational quantum chemistry has been increasingly employed toward rationalizing the

stereochemical outcome of a diverse range of reactions1 The approach typically involves the

identification of kinetically significant transition states and intermediates In our laboratory ab

initio as well as DFT methods are employed to gain insights into carbon-carbon and carbon-

heteroatom bond-forming reactions of immediate practical significance2 The key objective is in

establishing the factors responsible for stereoselectivity in such reactions and to employ those

insights toward in silico design of novel catalysts for potential asymmetric applications3

A number of examples wherein the conventional transition state models required systematic

improvements toward accounting the observed product distribution and stereochemical outcome

will be presented In general the presentation would encompass a few contemporary themes in the

domain of organo- and organo-metallic catalysis Interesting interpretationsrationalizations of

experimental observations besides meaningful guidelines for rational improvements in asymmetric

catalysis would remain the key focus of the presentation The contents are designed to cater to a

broad and diverse group of audience hence the chemical insights would receive more emphasis

rather than intricate technical details

[1] (a) Cheong P H ndashY Legault C Y Um J M Celebi-Olcum N Houk K N Chem Rev

2011 111 5042 (b) Sunoj R B Wiley Interdisciplinary Reviews Comput Mol Sci 2011 1

920

[2] (a) Shinisha C B Sunoj R B J Am Chem Soc 2010 132 12135 (b) Sharma A K

Sunoj R B Angew Chem Int Ed 2010 49 9373 (c) Sharma A K Sunoj R B Chem

Commun 2011 47 5759 (d) Jindal G Sunoj R B Chem Eur J 2012 18 7045 (e) Jindal

G Sunoj R B Angew Chem Int Ed 2014 53 4432 (f) Anand M Sunoj R B Schaefer

H F J Am Chem Soc 2014 136 5535

[3] (a) Shinisha C B Sunoj R B Org Biomol Chem 2007 5 1287 (b) Shinisha C B Sunoj

R B Org Lett 2009 11 3242 (c) Jindal G Sunoj R B Org Bimol Chem 2014 12 2745

49

IL26

CATALYTIC ASYMMETRIC CROTYLATION METHOD DEVELOPMENT

AND APPLICATION IN TOTAL SYNTHESIS

AV Malkov PS Orsquohora CA Incerti-Pradillos MA Kabeshov

Loughborough University Loughborough LE11 3TU UK

Secondary metabolites 1-5 isolated from marine soft coral Pseudopterogorgia elisabethae exhibit a

wide range of useful biological properties which include anti-tubercular anti-inflammatory

antimicrobial and analgesic activities [1] The analgesic properties are superior to the existing

industry standards As a result partially purified gorgonian extracts are used in commercial skin

care products for topical applications [2]

H

OH

HO

Pseudopterosin A-Daglycone

H H

O

O

HO

H

OH

O

O

H

O

O

HO

HH

1 2 3 4

(ndash)-Elisapterosin B (ndash)-Colombiasin A(+)-Elisabethadione(+)-Erogorgiaene

5

Herein we present a novel general strategy for a scalable enantioselective total synthesis of

serrulatane diterpenes 1 and 2 Synthetically a major challenge associated with the synthesis of

these compounds is the control of the three stereocentres in the absence of directing functional

groups Our principal strategy is based on the asymmetric crotylation of cinnamyl-type aldehyde 10

with Z-crotyltrichlorosilane 9 to produce homoallylic alcohol 8 with a set of stereogenic centers that

will be used to control the stereochemistry of oxy-Cope rearrangement (8 rarr 7) and the subsequent

transformations towards the advanced intermediate 6 Development of novel efficient Lewis base

catalysts for the asymmetric crotylation and completion of the total synthesis of (ndash)-elisabethadione

and (ndash)-erogorgiaene will be discussed in detail

SiCl3O

OH

Cat

H

O

Anionic oxy-Cope

H

OH6

cationic cyclisation

Wittigolefination

12

7

810

Rn

Rn

RnRn

1

4

11

9

References

[1] A D Rodriguez C Ramirez J Nat Prod 2001 64 100-102

[2] A Kijjoa P Sawanwong Mar Drugs 2004 2 72-82

50

IL27

SYNTHESES OF METAL COMPLEXES WITH TRANS-CYCLOALKANE-

12-DIYL-[OSSO]-TYPE BIS(PHENOLATE) LIGAND AND ISOSPECIFIC

POLYMERIZATION OF ALPHA-OLEFINS

A Ishii

Department of Chemistry Graduate School of Science and Engineering Saitama University

Shimo-okubo Sakura-ku Saitama 338-8570 Japan

Efficiency and stereoselectivity of reactions catalyzed by metal complexes are often greatly affected

by auxiliary ligands of the catalysts We have recently developed tetradentate auxiliary ligands 1

featuring oxygen and sulfur coordination sites and fusion of trans-cycloalkane-12-diyl rings1ndash3

The

[OSSO]-bis(phenolate) ligand 1 (n = 3) was applied to the synthesis of zirconium complex 2 and we

found that a combination of 2 and an activator catalyzes the polymerization of 1-hexene with high

activity and high isospecificity1 in comparison with previously reported group 4 metal complexes

bearing [OSSO]-type ligands4 We have also synthesized Ti

5 Zr

6 Hf

7 V

8 Nb

8 Ta

8 and Al

9

complexes with 1 (n = 3) and investigated catalytic reactions with these complexes In this paper

we report the syntheses and structures of these metal complexes and their catalytic ability with

recent progress

S

SO

tBu

tBu

O

tBu

tBu

ZrCH2Ph

CH2Ph

1 2

S OH

tBu

tBu

OH

tBu

tBu

Sn

Bu 2(Ph3C)[B(C6F5)4] Bu Bu Bu Bu Bu

isotactic poly(1-hexene) ([mmmm] gt95)

activity =

2500 gbullmmolndash1bullhndash1

Mw = 59000 PDI = 17

References

1 Ishii A Toda T Nakata N Matsuo T J Am Chem Soc 2009 131 13566ndash13567

2 Ishii A Toda T Nakata N Matsuo T Phosphorus Sulfur Silicon 2011 186 1169ndash1174

3 Ishii A Asajima K Toda T Nakata N Organometallics 2011 30 2947ndash2956

4 Nakata N Toda T Ishii A Polym Chem 2011 2 1597ndash1610

5 Nakata N Toda T Matsuo T Ishii A Inorg Chem 2012 51 274ndash281

6 Toda T Nakata N Matsuo T Ishii A J Organomet Chem 2011 696 1258ndash1261

7 Nakata N Toda T Matsuo T Ishii A Macromolecules 2013 46 6758ndash6764 Nakata N

Saito Y Watanabe T Ishii A Top Catal 2014 57 918ndash922

8 Toda T Nakata N Matsuo M Ishii A ACS Catal 2013 3 1764minus1767

9 Nakata N Saito Y Ishii A Organometallics 2014 33 1840ndash1844

51

IL28

NEW APPROACH FOR THE SYNTHESIS OF COMPOUNDS CONTAINING

CF2 FRAGMENT

AD Dilman VV Levin AA Zemtsov MD Kosobokov

N D Zelinsky Institute of Organic Chemistry

Existing methods for the synthesis of compounds containing CF2 fragment either employ hazardous

reagents or require long synthetic sequence We propose a new approach towards difluorinated

compounds based on the coupling of three components mdash nucleophile difluorocarbene and

electrophile

As nucleophiles organometallic reagents can be employed The insertion of difluorocarbene into

carbon-zinc bond of organozinc reagents leads to new organozinc species which can be quenched

by halogen or proton1 or coupled with allylic electrophiles

2

The interaction of trimethylsilyl cyanide with difluorocarbene affords difluoro(trimethylsilyl)-

acetonitrile This reagent was used in reactions with aldehydes and imines furnishing fluorinated

alcohols and amines3 The addition products can be transformed into a variety of heterocyclic

molecules4

This work was supported by the Ministry of Science (project MD-475020133) and Russian

Foundation for Basic Research (projects 13-03-12074 14-03-00293 14-03-31253_mol_a 14-03-

31265_mol_a)

1 Levin V V Zemtsov A A Struchkova M I Dilman A D Org Lett 2013 15 917ndash919

2 Zemtsov A A Kondratyev N S Levin V V Struchkova M I Dilman A D J Org

Chem 2014 79 818ndash822

3 Kosobokov M D Dilman A D Levin V V Struchkova M I J Org Chem 2012 77

5850ndash5855

4 Kosobokov M D Struchkova M I Arkhipov D E Korlyukov A A Dilman A D

J Fluorine Chem 2013 154 73ndash79

52

IL29

TOWARDS REALISTIC FIRST-PRINCIPLES MODELLING OF

COMPLEXITY IN HETEROGENEOUS CATALYSIS

KM Neyman

ICREA and Universitat de Barcelona

Active components present in heterogeneous catalysts as nano-aggregates of thousands atoms

remain inaccessible for the first-principles (based on DFT) computations due to their size and

complexity However such species could be rather realistically represented by computationally

tractable smaller model nanoparticles (NPs) whose surface sites only marginally change the

reactivity with increasing particle size We illustrate this for decomposition of methane1 and

methanol2-4

on Pt and Pd catalysts as well as building of active sites on Ptceria catalysts56

We

show that using common slab models and thus neglecting the nanoscopic effects in these and

similar systems could lead to severe misrepresentation of the surface reactivity7

Methane decomposition on Pt NP is calculated to be more exothermic than on Pt(111) surface and

proceed via much lower activation barriers for the rate-limiting steps1 The reason for Pt activation

by nanostructuring is that CHx species are stabilized on NP edges converting the first two steps of

CH4 decomposition from endothermic on Pt(111) to exothermic on Pt79 The higher activity of edge

Pt atoms was assigned to their lower coordination and higher flexibility

The flexibility affects not only adsorption properties of sites with low-coordinated atoms but also

nearby terrace sites This effect is most pronounced for strongly bound adsorbates eg atomic C It

is a common by-product in decomposition reactions on Pd2 able to modify catalyst properties upon

exothermic migration subsurface34

The most spectacular effect of flexibility of Pd NPs is on the

subsurface migration barriers of surface C Near NPs edges these barriers essentially vanish

Presence of subsurface C makes Pd NPs more transparent for subsurface diffusion of adsorbed

hydrogen3 which in turn enables sustainable hydrogenation of olefins on Pd catalysts

Strong metal-support interactions can radically modify surface chemistry Due to catalysts

complexity the microscopic origin of such effects is usually unresolved However our study on

models of Pt-ceria catalysts succeeded to uncover atomic details of interactions in this system5

Calculations identified two types of oxidative Pt-ceria interactions electron transfer from a Pt

particle to the support and O transport from ceria to Pt The former is favorable on ceria supports

regardless their morphology But the O transfer requires the presence of Pt in close contact with

nanostructured ceria being inherently a nano-effect Both effects were detected by monitoring the

Ce3+

Ce4+

ratio using resonant photoelectron spectroscopy on Pt-CeO2 model catalysts

These case studies reveal very significant differences in the surface reactivity derived from

customary slab-model calculations and those employing dedicated NP models The latter expose a

variety of active sites whose structure and geometric flexibility notably better match those of the

sites present under experimental conditions Thus we advocate much broader usage of suitable NP

models in ldquocatalysis from first principlesrdquo 1 F Vintildees Y Lykhach T Staudt M P A Lorenz C Papp H-P Steinruumlck J Libuda K M Neyman A Goumlrling -

Chem Eur J 2010 16 6530

2 I V Yudanov A V Matveev K M Neyman N Roumlsch - J Am Chem Soc 2008 130 9342

3 K M Neyman S Schauermann - Angew Chemie Int Ed 2010 49 4743

4 H A Aleksandrov F Vintildees W Ludwig S Schauermann K M Neyman - Chem - Eur J 2013 19 1335

5 G N Vayssilov Y Lykhach A Migani T Staudt G P Petrova N Tsud T Skaacutela A Bruix F Illas K C Prince

V Matoliacuten K M Neyman J Libuda - Nature Mater 2011 10 310

6 A Bruix Y Lykhach I Matoliacutenovaacute A Neitzel K C Prince V Potin F Illas V Matoliacuten J Libuda K M

Neyman et al - Angew Chemie Int Ed 2014 53 doi 101002anie201402432

7 S M Kozlov K M Neyman - Top Catal 2013 56 86

53

IL30

С-С TRIPLE BOND ACTIVATION BY PLATINUM METALS UNDER

HOMO- AND HETEROGENEOUS CONDITIONS DESIGN OF NEW

CATALYTIC REACTIONS

SA Mitchenko

LM Litvinenko Institute of Physical Organic and Coal Chemistry National Academy of Sciences

of Ukraine Donetsk Ukraine

Petroleum and natural gas are the main sources of raw materials for modern bulk and fine chemical

industry Since the middle of the last century this changed the industry redirecting technology

previously based on acetylene towards olefinic stuff and synthesis gas Nevertheless series of large-

scale (for example manufacture of vinyl ethers pyrrolidone and N-methylpyrrolidone butanediol

etc) and fine (drugs and fragrances crop protecting agents etc) chemical production based on

acetylene hydrocarbons possesses definite advantages and is still developing Besides acetylene

hydrocarbons are inevitably formed as by-products in oil processing yielding olefins and taking

into account the modern industrial scales and prices of starting materials these by-products should

be efficiently utilized On the other hand coal and natural gas supply as against of petroleum allow

us to regard them as practically inexhaustible source of acetylene Increasing interest to the catalytic

chemistry of acetylene (see for example [1 2]) can be motivated in particular by these

considerations

Results of development of new catalytic transformations of acetylene under homo- and

heterogeneous conditions will be presented and discussed

References

1 Alonso F Beletskaya IP Yus M Chem Rev 2004 104 3079

2 Ananikov V P Beletskaya I P Organometallics 2012 31 1595

54

IL31

SYNERGISTIC EFFECTS IN DESIGNING COMBINED CATALYTIC

SYSTEMS (COMBICATrsquoS) FOR ABATEMENT OF

NITROGEN OXIDES (NOX)

AYu Stakheev

Zelinsky Institiute of Organic Chemistry Catalysis division Moscow Russia

Anthropogenic emission on nitrogen oxides (NOx = NO NO2 N2O) becomes an important issue

since the amount of anthropogenic NOx nowadays exceeds biogenic emission (~110 Mt vs 80

Mtannual) and their impact on environment is significant The most effective method for

abatement of nitrogen oxides is their selective catalytic reduction (SCR) by urea or NH3

2NO + 2NH3 + 12O2 = 2N2 + 3 H2O

However activity of the traditional NH3-SCR catalysts at the temperatures below 250oC is not

sufficient due to the stringent restrictions imposed by environmental legislations on NOx emission

from mobile sources The effective solution can be provided by Cu-containing zeolite catalyst

however high cost often limits their practical application Our recent study revealed alternative

approach and indicated that promising NH3-DeNOx activity at Treact lt 250degC CAN BE ATTAINED OVER

combined catalysts (CombiCat) comprising zeolite component (possessing high activity in SCR)

and a redox component (having high activity in NO oxidation) For such compositions we found a

pronounced synergistic effect and the catalytic activity of the COMBICATrsquoS significantly exceeds

activity of the individual components A number of compositions have been tested for searching

synergistic effects and the most remarkable results have been observed for [CuAl2O3 +FeBETA]

[MnAl2O3 + FeBETA [CeZr +FeBETA] [MnCeZr + FeBETA] MnFeBETA Interestingly that

the studied composition exhibits favorable performance in selective oxidation of NH3

2NH3 + 32 O2 = N2 + 3H2O

Therefore CombiCatrsquos are capable to accomplish two functions SCR catalyst and removal of

residual NH3 In addition to that for the compositions comprising CeO2-ZrO2 component a

promising soot oxidation activity has been observed

Detailed study of a possible origin of the observed synergistic effects suggests that the improvement

of NH3-DeNOx activity can be attributed to a ldquodual functionrdquo reaction mechanism comprising two

main stages

(1) NO + O2 harr NO2 over redox component

(2) NO + NO2 + 2NH3 rarr N2 + 3H2O over zeolite component

However further research is required for revealing overall reaction network and understanding

reaction mechanism responsible for observed synergy

55

IL32

NOVEL COLCHICINOIDS AS POTENTIAL ANTITUMOR AGENTS

A Yu Fedorov

Department of Organic Chemistry Nizhny Novgorod State University Gagarina av 23 Nizhny

Novgorod 603950 Russian Federation

A range of indole - and furane-containing allocolchicinoids was synthesized

Several from synthesized compounds manifested high in vitro and in vivo antitumor activity

Acknowledgment

We thank the Russian Foundation for Basic Research (projects 14-03-91342 and 12-03-00214-a)

The Ministry of Education and Science of The Russian Federation (project 46192014K) The

research is partly supported by the grant 02В49210003 of The Ministry of Education and

Science of the Russian Federation to Lobachevsky State University of Nizhni Novgorod

56

IL33

ENANTIOSELECTIVE CATALYSIS BY CHIRAL BROslashNSTED ACIDS AND

CHIRAL BRШNSTED BASES

M Terada

Tohoku Univsersity Department of Chemistry Sendai Japan

Chiral phosphoric acids 1 have become one of the most versatile types of chiral Broslashnsted acid

catalysts identified to date and have been applied to a broad range of enantioselective

transformations12)

In my continuing efforts to broaden the scope of enantioselective catalysis by 1

activation of oxygenated functional groups other than imines and related functional groups is our

recent research interest To expand the scope of chiral Broslashnsted acid catalysis recently a novel

chiral bis-phosphoric acid 2 was developed as a highly active and efficient enantioselective

catalyst3)

On the other hand intense interest has been devoted to the development of chiral

uncharged organosuperbase catalysts during the past decade In an effort to develop efficient chiral

organobase catalysts we designed and synthesized unique axially chiral Broslashnsted base 34)

3

functioned as the efficient enantioselective catalysts for the activation of pro-nucleophile having a

relatively acidic proton such as 13-dicarbonyl compounds To expand the scope of chiral Broslashnsted

Base catalysis development of much stronger organosuperbase is highly demanded We hence

designed a pseudo C2-symmetric bis(guanidino)iminophosphorane 4 as a novel family of chiral

organosuperbases5)

In my presentation I briefly introduce these chiral Broslashnsted acid catalysts (1

and 2) and base catalysts (3 and 4) In particular I would like to present a novel chiral Broslashnsted

base catalyst 4 in details

References

1) (a) Terada M Synthesis 2010 1929-1982 (b) Terada M Chem Commun 2008 4097-4112

2) Uraguchi D Terada M J Am Chem Soc 2004 126 5356-5357

3) Momiyama N Konno T Furiya T Iwamoto T Terada M J Am Chem Soc 2011 133

19294-19297

4) Terada M Ube H Yaguchi Y J Am Chem Soc 2006 128 1454-1455

5) Takeda T Terada M Y J Am Chem Soc 2013 135 15306-15309

57

IL34

IONIC LIQUIDS WATER AND LIQUID OR SUPERCRITICAL CO2 AS

PERSPECTIVE MEDIA FOR ASYMMETRIC ORGANOCATALYSIS

SG Zlotin

ND Zelinsky Institute of Organic Chemistry Russian Academy of Sciences

Over the last decade amazing results have been associated with the extensive application of

asymmetric organocatalysts in organic synthesis In the presence of small metal-free chiral organic

molecules (α-amino acid or cinchona alkaloid derivatives BINOL phosphoric acids and other

chiral compounds) available prochiral reagents can be easily converted into chiral products of high

molecular complexity in high yields and with excellent enantioselectivities Unlike organometal

catalysts organocatalysts do not contaminate products with toxic heavy metals and this is important

in terms of medicinal chemistry However in some cases they may be responsible for hardly

separable and potentially dangerous organic impurities

To facilitate product purification and recovery of precious chiral catalysts immobilized forms of

organocatalysts tagged to polymers or ionic groups have been designed and organocatalytic

reactions have been carried out in so called ldquoneotericrdquo green solvents particularly in ionic liquids

(IL) water and liquid or supercritical (sc) carbon dioxide In these systems a catalyst and a product

are located in different phases during the catalytic process andor the working-up step

We developed highly efficient enantioselective cross-aldol reactions between various carbonyl

compounds in the presence of proline or prolinamide-derived organocatalysts in the IL andor

aqueous environment An original method for adapting -amino acid-sourced IL-supported chiral

organocatalysts to the aqueous medium via an incorporation of long-chain alkyl groups and

hydrophobic anions into their molecules and by performing asymmetric reactions in reagentswater

two-phase systems was elaborated Corresponding aldol products were obtained in high yields and

with extremely high anti -diastereo- (dr up to 98 2) and enantioselectivities (ee up to 99) under

proposed conditions After product isolation the remaining catalyst-water heterogeneous system

could be reused up to 15 times without a decrease of product yield and selectivity of the reaction1

Carbon acids in particular malonates malononitrile and anthranone appeared to react

enantioselectively with nitroalkenes in the presence of tertiary aminethiourea-derived bifunctional

organocatalyst in liquid CO2 as a green substitute of toxic organic solvents to afford the respective

Michael adducts in moderate to high yields and with enantioselectivities of up to 92 ee2 The first

ldquogreenrdquo asymmetric organocatalytic reaction in sc-CO2 namely a bifunctional squaramide-

catalyzed addition of diphenylphosphite to α-nitroalkenes to afford β-nitrophosphonates in high

yields and with ee-values of up to 94 was elaborated3 In this way the most active (R)-enantiomer

of the therapeutically useful GABAB receptor agonist baclofen a key precursor of the chiral

anticonvulsant pregabalin and both enantiomers of pharmacologically important β-amino

phosphonic acid derivatives were synthesized A significant potential of the supercritical extraction

for product isolation and catalyst recovery which completely eliminates the use of organic solvents

during the working-up procedure was demonstrated

The work was financially supported by the Russian Foundation of Basic Research (projects 12-03-

00420 14-03-31321 and 14-03-92701)

1 DE Siyutkin AS Kucherenko SG Zlotin In ldquoComprehensive Enantioselective

Organocatalysis Catalysts Reactions and Applicationsrdquo ed by PI Dalco Wiley-VCH 2013

v 2 p 617-650

2 AG Nigmatov IV Kuchurov DE Siyutkin SG Zlotin Tetrahedron Lett 2012 53 3502

3 IV Kuchurov AG Nigmatov EV Kryuchkova AA Kostenko AS Kucherenko SG

Zlotin Green Chem 2014 16 1521

58

IL35

MAKING OLEFIN METATHESIS WORK - RECENT RESULTS IN

RUTHENIUM CATALYSTS DESIGN

KL Grela

Biological and Chemical Research Centre Faculty of Chemistry University of Warsaw

Ruthenium-catalyzed olefin metathesis reactions represent an attractive and powerful

transformation for the formation of new carbon-carbon double bonds [1] This area is now quite

familiar to most chemists as numerous catalysts are available that enable a plethora of olefin

metathesis reactions [1] However formation of substituted and crowded double bonds decreasing

the amount of metal using metathesis in green context etc still remain a challenge making

industrial applications of this methodology difficult [2] These limitations can be solved by

designing new more active and stable catalysts and catalysts that can be easier removed recycled

[3]

During the lecture a number of representative examples will be presented

Artwork copy Katarzyna Felchnerowska wwwfbcomeffefineart

References

[1] Olefin Metathesis Theory and Practice Grela K (Ed) John Wiley amp Sons 2014

[2] Thayer A Chemical amp Engineering News 2007 85 (07) 37

[3] Clavier H Grela K Kirschning A Mauduit M Nolan S P Angew Chem Int Ed 2007

46 6786-6801

59

60

Oral Communications

61

62

OC1

THE FIRST CYCLOPENTADIENYL NICKEL COMPLEXES BEARING A

SILYL GROUP OR HYDROGEN SUBSTITUTED PHOSPHINE

CHELATING SIDECHAIN

I Werner H Butenschoen

Institute of Organic Chemistry Leibniz Universitaet Hannover Hannover Germany

The only known secondary phosphine pendant cyclopentadienyl complexes are those of zirconium

and hafnium reported by Ishiyama et al in 2002[1]

Since these complexes contain a reactive

phosphorus-hydrogen bond they were converted into the corresponding phosphide-substituted

cyclopentadienyl chelate complexes[2]

Both systems were successfully applied in catalytic ethylene

and styrene polymerization reactions as well as in ethylenestyrene copolymerization reactions[3]

To our knowledge no analogous complexes of late transition metals containing a phosphorus-

hydrogen or a phosphorus-silyl bond have so far been reported We report on the synthesis of the

first cyclopentadienyl nickel complexes 1-4 and 5 7 bearing a silyl group and hydrogen substituted

phosphine chelating sidechain respectively

Treatment of complex 5 with SIMes induced the decomplexation of the secondary phosphane

substituted tether delivering exclusively nickel carbene complex 6

Recrystallization of complex 7 from hexaneethyl acetate (11) at 30 degC afforded crystals suitable

for an X-ray crystal structure analysis

References

[1] T Ishiyama H Nakazawa K Miyoshi J Organomet Chem 2002 648 231

[2] T Ishiyama T Mizuta K Miyoshi H Nakazawa Organometallics 2003 22 1096

[3] T Ishiyama K Miyoshi H Nakazawa J Mol Cat A-Chem 2004 221 41

63

OC2

EXPANDED RING N-HETEROCYCLIC CARBENE TRANSITION METAL

COMPLEXES SYNTHESIS STRUCTURE APPLICATIONS IN

CATALYSIS

MS Nechaev1 AF Asachenko

2 PB Dzhevakov

2 OS Morozov

2 GV Proskurin

1 PS

Gribanov1

1 - Moscow State University Department of Chemistry Moscow Russia

2 - A V Topchiev Institute of Petrochemical Synthesis RAS Moscow Russia

N-heterocyclic carbenes (NHCs) became widely used as organocatalysts and as ligands in transition

metal catalysis Most of NHC-metal complexes known to date are derived from five-membered ring

imidazol-2-ylidene and imidazolin-2-ylidene type carbenes In recent years our group develops

chemistry of 6- 7- and 8-membered ring carbenes Expanded ring carbenes (er-NHCs) exhibit

superior stereoelectronic properties in comparison with five-membered ring counterparts

Expansion of the ring leads to significant increase in donor strength and sterical hindrance

In this contribution we report our recent results on theoretical calculations of electronic structure

and ligand properties of er-NHCs efficient methods of synthesis of precursors and generation of

free carbenes synthesis of late transition metal (Cu Ag Au Pd) complexes It was found that er-

NHC complexes of palladium are highly active in Suzuki-Miyaura coupling in water and

dimerization of terminal alkynes with formation of E-enynes Cationic gold complexes are active

catalysts of addition of nucleophiles to carbon-carbon triple bonds

64

OC3

PALLADIUM-CATALYZED CndashH ALKENYLATION OF ARENES USING

SULFUR-CONTAINING DIRECTING GROUPS A COMPARATIVE STUDY

KV Luzyanin AN Marjanov VP Ananikov

Laboratory of Cluster Catalysis Saint Petersburg State University Universitetsky pr 26 Stary

Petergof 198504 Russia

Direct alkenylation of organic substrates via directing-group assisted functionalization of the CH

bond has emerged as a valuable tool for creation of new sp2-sp

2 bonds In the contrast to the

MirozokindashHeck reaction that starts from the aryl halides this procedure works with inactivated

arenes and is favorable from both economical and environmental points of view Several types of

directing groups have been evaluated in the direct alkenylation up to date eg ketones and

carboxylates amides pyridine sulfoxides and ethers and thioethers Among them functionalization

of sulfur-containing compounds (Scheme 1) ie pyridine thioesters and sulfoxides as well as

structurally related benzylic thioethers (in those sulfur moiety plays a role of a directing group)

attracts rapidly growing attention On the one hand functionalization of such compounds leads to

interesting derivatives containing both alkene and sulfur functions while on the other hand sulfur-

based directing groups in these species can be easily removed after reaction from the resulting

products without compromising other functionalities1ndash3

Scheme 1 Direct alkenylation of arenes using sulfur-containing directing groups

In the current report we summarize data accumulated up to date regarding direct CH-alkenylation

of sulfur-containing organic compounds A particular emphasis is given to the evaluation of the

assistance provided by different sulfur-containing directing groups in comparison to other common

directing moieties known to be employed for this purpose

Acknowledgements This work has been partially supported by the Saint Petersburg State

University (research grant from Laboratory of Cluster Catalysis) and the Russian Fund for Basic

Research (grant 14-03-01005)

References 1 Garciacutea-Rubia A Fernaacutendez-Ibaacutenez M A Goacutemez Arrayaacutes R Carretero J C Chem Eur J

2011 17 3567ndash3570

2 Yu M Xie Y Xie C Zhang Y Org Lett 2012 14 2164ndash2167

3 Zhang X-S Zhu Q-L Zhang Y-F Li Y-B Shi Z-J Chem Eur J 2013 19 11898ndash

11903

65

OC4

IN PURSUIT OF A NOVEL IMIDATE-BASED SALEN-TYPE LIGAND

CLASS

J Van Der Eycken1 P Janssens

1 T Noel

2

1 - Ghent University Department of Organic Chemistry

2 - Eindhoven University of Technology Department of Chemistry and Chemical Engineering

Micro Flow Chemistry amp Process Technology

An increasing ecological awareness and global competitiveness have challenged the chemical

industry towards a higher level of sustainability through innovation and technology In research the

majority of topics on sustainable process development deals with catalysis[1]

Furthermore in

organic synthesis transition metal catalysis already plays a vital role in the synthesis of biologically

active compounds[2]

N N

OH HO

N N

H H H HO O

OH HO

L1 L2

Bisimidate ligand L2 shows striking similarities with Salen ligands (L1) We reasoned that this

could open new opportunities for our already well-established imidate ligand family [3-5]

Nevertheless the applicability of this ligand in the MnV-catalyzed asymmetric epoxidation reaction

turned out to be more complicated than expected

In this communication the search towards an effective novel imidate-based Salen-type ligand class

will be discussed from a ligand design point of view

References

[1] Dichiarante V Ravelli D Albini A Green Chem Lett Rev 2010 3 105

[2] a) Noyori R Angew Chem Int Ed 2002 41 2008 b) Busacca CA Fandrick DR Song

JJ Senanayake CH Adv Synth Catal 2011 353 1825

[3] a) Noeumll T Bert K Van der Eycken E Van der Eycken J Eur J Org Chem 2010 21

4056 b) Bert K Noeumll T Van der Eycken J Org Biomol Chem 2012 10 8539 c) Noeumll T

Bert K Janssens P and Van der Eycken J (2012) ldquoChiral Imidate Ligands Synthesis and

Applications in Asymmetric Catalysisrdquo in Innovative Catalysis in Organic Synthesis

Oxidation Hydrogenation and C-X Bond Forming Reactions (ed P G Andersson) Wiley-

VCH Verlag GmbH amp Co KGaA Weinheim Germany doi 1010029783527646586ch14

66

OC5

NITROALKANES IN PPA AS NEW REAGENTS FOR DIRECT METAL-

FREE AMINATION OF ARENES

AV Aksenov1 NA Aksenov

1 IV Aksenova

1 M Rubin

2 DA Aksenov

1

1 - Department of Chemistry North Caucasus Federal University Stavropol Russian Federation

2 - Department of Chemistry University of KansasLawrence USA

Aromatic amines represent an important class of organic compounds Many of them demonstrate

important biological activities Various multi-step methods for preparation of these compounds

have been developed including electrophilic nitrationreduction sequence Schmidt and Beckmann

rearrangements etc The most appealing methods however are those that allow for direct

introduction of an amino-group to a non-substituted arene over a single step

Direct electrophilic acetamidation of arenes 2 with primary nitroalkanes 1 in polyphosphoric acid

(PPA) recently developed in our laboratories can be viewed as an example of such an approach

R

N+

O

O

P P A

R

N+

O

O P

O

O H

O R

2

R3

R1

R4

R2

N

R

O

PO

O H

O

R3

R4

R1

R2

NH

R

OR3

R1

R4

6 3 -9 2

2

1

3 R=Me Pr Ph Bn R

1 R

2 R

3 R

4=H Me OH MeO CHO

Benzene and arenes with electron-donating substituents can be engaged in this reaction Electron

deficient arenes are inert The process is highly selective the electrophilic attack is always directed

to para-position with respect to a substituent already present in the ring

Anthracene 4 and indole 5 were successfully involved into the acetamidation reaction In reaction of

dibenzo-18-crown-6 ether monoacetamide was formed along with quite a large amount of bis-

acetamination isomeric products

The reaction involving secondary nitroalkanes is also interesting Since the nitroso compound 4

resulting from electrophilic attack to the aromatic ring is not able to isomerize oxime it attacks a

second molecule of arene After rearrangement this leads to the formation of diarylamines 5

N+ O

O P O2H

- H +N

O H

O P O2H

R1

R2

P P A

O

R1

R2

NO

R1

R2

- H2O R

1

R2

N

O HR

1

R2

R1

R2

R1

R2

N

O H

R1

R2

R1

R2

NH

+-P P A

+

4

5 5 5 -6 1 R

1 R

2 =H Me MeO CHO

A novel protocol for direct and regioselective metal-free acetamination and amination of arenes in

reactions with primary and secondary nitroalkanes in polyphosphoric acid media was developed A

new preparative approach to 5-aminoindoles and diarylamines employing this reaction was

demonstrated

This work was carried out with financial support from the Russian Foundation Basic Research

(grants 13-03-00304 a and 14-03-31288 mol_a)

67

OC6

UROTROPINE ISOMER (14610-TETRAAZAADAMANTANE)

MOLECULAR SIMPLICITY AND MOLECULAR COMPLEXITY OF

HETEROADAMANTANE CAGE

AYu Sukhorukov AN Semakin IS Golovanov SL Ioffe VA Tartakovsky

ND Zelinsky Institute of Organic Chemistry Moscow Russia

For more than 100 years heteroadamantanes have been objects of rapt attention for fundamental

and applied chemistry These cage polycyclic systems represent interest not only due to their unique

properties but also as convenient models for the study of basic problems dealing with structure and

reactivity of organic compounds Among many heteroadamantanes 1357-tetraazaadamantane

(urotropine) which was first obtained by A Butlerow in 1859 plays probably the most important

role from an applied point of view Urotropine is widely used in medicine polymer production

food industry as well as organic synthesis coordination chemistry and MOFs design This simplest

Td-symmetrical 1357-tetraazaadamantane is the only known representative of the class of

tetraazaadamantanes In this context the possibility of existence of other tetraazaadamantanes

isomeric to urotropine represents considerable fundamental interest

The present report deals with the first synthesis of 14610-tetraazaadamantane (ldquoisourotropinerdquo)

the C3v-symmetrical structural isomer of urotropine and a series of its derivatives (see Figure) X-

Ray and quantum-chemical studies demonstrate remarkable distinctions in structures of urotropine

and ldquoisourotropinerdquo cages probably arising from different types of lp(Neq) C N interactions in

these heterocage systems Since substitution at bridge and bridgehead nitrogen atoms can be easily

installed 14610-tetraazaadamantane can be considered as a new rigid multivalent (3+1) scaffold

for the design of complex functional molecules and materials

Acknowledgement

The financial support from RFBR (grant 14-03-00933a) and Russian Presidentrsquos Council for Grants

(grant MK-391820133) is greatly acknowledged

68

OC7

PALLADIUM-CATALYZED CROSS-COUPLING REACTION OF

ALCOHOL WITH ARYL CHLORIDE THROUGH C-C BOND ACTIVATION

C-H Jun H-S Park D-S Kim

Yonsei University Department of Chemistry Seoul South Korea

The C-C bond activation is one of challenging subjects in organometallic chemistry1 Especially

catalytic version of C-C bond activation has been recently achieved by chelation assisted transition

metal catalyst consisted of Rh(I) and 2-amino-3-picoline2 During the course of our studies on

these types of C-C bond activation we found decarbonylative esterification of aliphatic alcohol

with aryl chloride by palladium metal as shown below For example when the reaction of

chlorobenzene and 1-naphtylethanol was carried out at 150oC under PdC and NaF base a mixture

of three products 1-naphtylethyl benzoate ester benzene and 1-methylnaphthalene was obtained

in reasonable yields

The reaction mechanism is proposed as follows The reaction proceeds through several consecutive

reactions Initially primary alcohol is oxidized by aryl chloride to aldehyde with formation of aryl-

H under palladium catalyst Aldehyde is decarbonylated by Pd to generate alkane and (CO)Pd The

intermediate (CO)Pd is oxidatively added to aryl chloride to form acyl-PdCl complex which reacts

with alcohol to give ester compounds In this reaction reactivity of substrate should be well

balanced The reactivity of chloroarene is suited for this purpose since other aryl halide such as

bromobenzene and iodobenzene did not show any reactivity in this reaction This result is quite

interesting since aryl chloride is least reactive for common C-C bond coupling reaction while aryl

iodide is very reactive The reaction works well with aryl chloride One of merits in this protocol is

that carbonylation proceeds without using toxic CO gas and CO source is non-toxic alcohol More

detailed mechanistic studies using 13

C-enriched or deuterated alcohol will be discussed

References

1 Jun C -H Chem Soc Rev 2004 33 610-618

2 Park Y J Park J -W Jun C -H Acc Chem Res 2008 41 222-234

69

OC8

RADICAL-CATIONS OF ACETYLENE COMPOUNDS IN CARBON-

CARBON BOND FORMING REACTIONS

AV Vasilyev

Saint Petersburg State Forest Technical University Institutsky per 5 Saint Petersburg 194021

Russia Saint Petersburg State University Institute of Chemistry

Radical-cations of acetylene compounds A generated under oxidation of alkynes I in systems

PbO2-strong acid (CF3CO2H HF HSO3F) are key reaction intermediates in various new carbon-

carbon bond forming processes [1-6]

Depending on structure the species A lead to formation of a variety of products II-VII When

substituents X are moderate electron acceptors CO2R COAr COR PO(OEt)2 trans-ethenes II are

stereoselectively formed In case of stronger acceptors furan derivatives III (X = COCF3

СОCO2Et) or diketones IV (X = CF3) are formed

In different acidic systems radical-cations of diarylacetylenes (X = Ar) give unsaturated diketones

V (in CF3CO2H) butadiene difluiorides VI (in HF) or dichlorides VII (in HSO3F followed by

quenching in HClaquaconc) The last ones are electro-cyclically converted into naphthalenes VIII

C

C C

C

Ar Ar

FF

Ar Ar

C C

Ar

C C

Ar

Cl Cl

Ar Ar

CC

C

O O

C

Ar Ar

ArAr

Cl

Ar

Ar

Ar

R

H+ = CF3CO2H

H+ = HF

1 H+=HSO3F 2 HCl

VI

VIII

X = COCF3

COCO2EtC

OX

C C

C

OC

Ar

Ar Y

C

OX

C C

C

OX

Ar

ArX = CO2Alk

COAr COMe

PO(OEt)2

C C X

C CAr

I

A

III

II-e

Ar

X

PbO2H+

CF3F3C

C C

C

O O

C ArArHH

X = CF3

Y = CF3 CO2Et

X = Ar

IVV

X = Ar

X = Ar

VII

[1] Vasilyev AV Rudenko AP Russ J Org Chem (in Engl) 1997 V33 P 1555-1584

[2] Shchukin AO Vasilyev AV Fukin GK Rudenko AP Russ J Org Chem (in Engl)

2007 V43 P1446-1450

[3] Vasilyev AV Aristov SA Fukin GK Kozhanov KA Bubnov MP Cherkasov VK Russ

J Org Chem (in Engl) 2008 V44 P 791-802

[4] Vasilyev AV Shchukin AO Walspurger S Sommer J Eur J Org Chem 2008 4632

[5] Vasilyev AV Rudenko AP Russ J Org Chem (in Engl) 2010 V46 P1282-1289

[6] Alkhafaji HMH Vasilyev AV Ryabukhin DS Rudenko AP Muzalevskiy VM

Nenajdenko VG Russ J Org Chem (in Engl) 2013 V49 P 621-623

70

OC9

ACTIVATION OF Ru-BASED OLEFIN METATHESIS CATALYSTS

A Poater1 L Cavallo

2

1 - Institut de Quimica Computacional i Catаlisi and Departament de Quimica Universitat de

Girona Campus de Montilivi E-17071 Girona Catalonia Spain

2 - Kaust Catalysis Center Physical Sciences and Engineering Division King Abdullah University

of Science and Technology Thuwal 23955-6900 Saudi Arabia

In recent years olefin metathesis catalyzed by N-heterocyclic carbene ruthenium complexes has

attracted remarkable attention as a versatile tool to form new C=C bonds[1] The last developed

(pre)catalysts show excellent performances and this achievement has been possible because of

continuous experimental and computational efforts to understand the laws controlling the behavior

of these systems This perspective talk rapidly traces the ideas and discoveries that computational

chemistry contributed to the development of these catalysts with particular emphasis on catalysts

presenting a N-heterocyclic carbene ligand Specifically one of the most important challenges in

ruthenium-catalyzed olefin metathesis is to increase the stability of the catalysts under reaction

conditions and this hopefully without loss of activity Special interest has been addressed to study

the activation of the second-generation Grubbs catalysts which has clarifier either a dissociative or

an interchange mechanism is feasible[2]

Although in the solid state most ruthenium-based olefin metathesis catalysts are stable to oxygen

and moisture in solution decomposition usually occurs readily Understanding the decomposition

routes of catalysts is extremely important as any insight gained in this area can guide catalyst design

efforts to participate then in the synthesis of drugs[34] Furthermore new challenging projects

plan to modify the structure of the NHC ligands or replace this ligand by alkylidene ligands and

even the substitution of the metal is a goal moving to more environmentally friendly metals

[1] G C Vougioukalakis R H Grubbs Chem Rev 110 1746 (2010)

[2] C A Urbina-Blanco A Poater T Lebl S Manzini A M Z Slawin L Cavallo S P Nolan

J Am Chem Soc 135 7073 (2013)

[3] S Manzini C A Urbina-Blanco A Poater A M Z Slawin L Cavallo S P Nolan Angew

Chem Int Ed 51 1042 (2012)

[4] S Manzini A Poater D J Nelson L Cavallo S P Nolan Chem Sci 5 180 (2014)

71

OC10

CHEMICAL REACTIVITY IN PROTEINS AND WATER QMMM MD

INSIGHTS INTO EFFECTS OF LOCAL STRUCTURAL ENVIRONMENTS

ON BOND CLEAVAGE

Y Zhao BJ Wang RB Wu ZX Cao

Department of Chemistry Xiamen University Xiamen 361005 China

Water and proteins play a quite important role in chemical and biological processes In past few

years we carried out a systematic investigation on the effect of local structural environments on

reactivity towards hydrolysis C-N C-O and C-H bond cleavages in proteins and water Using

Born-Oppenheimer ab initio QMMM MD simulations a state-of-the-art approach to simulating

enzymes we have investigated the structural features of zinc enzymes nucleoside hydrolase and

deaminase and plausible enzymatic mechanisms The molecular complexity of active domain in

enzyme and roles of conserved residues and protein environments in enzymatic catalysis have been

explored In particular the different coordination modes and fast ligand exchanges of zinc

coordination has been suggested to be one key catalytic feature of the zinc ion and the chelation

mode of hydroxamate with the zinc ion in HDACs is modulated by water access to the linker

binding channel This new insight into the interplay between the linker binding and the zinc

chelation emphasizes its importance for the development of new class-IIa-specific HDAC

inhibitors Our calculations indicate that the reliable theoretical treatment on the water-mediated

proton transfer and most hydrolysis reactions of carbonyl compounds such as aldehydes ketones

esters amides the carboxylic acids and their derivatives requires use of the large basis set and

suitable cluster-continuum model The effects of solvent and structural modification on hydration

and hydrolysis of carbonyl compounds have been discussed

Acknowledgements This work was supported by the National Science Foundation of China

(21133007 and 21373164) and the Ministry of Science and Technology (2011CB808504)

References

1 N Chen H Ge J Xu Z Cao and R Wu Biochim Biophys Acta 2013 1834 1117

2 R Wu W Gong T Liu Y Zhang and Z Cao J Phys Chem B 2012 116 1984

3 B Wang and Z Cao Chem Eur J 2011 17 11929

4 B Wang and Z Cao Angew Chem Int Ed 2011 50 3266

5 R Wu Z Lu Z Cao and Y Zhang J Am Chem Soc 2011 133 6110

6 Y Zhao N Chen R Wu and Z Cao 2013 submitted

72

OC11

MECHANISM OF INTRAMOLECULAR HECK REACTION BY DENSITY

FUNCTIONAL THEORY

A Ayyappan D Yogeswara Rao

Indian Institute of Technology Kharagpur Department of Chemistry West Bengal 721392 India

Heck Reaction the palladium-catalyzed C-C coupling between aryl halides or vinyl halides and

activated alkenes in the presence of a base is widely used in syntheric chemistry Intramolecular

version of Heck reaction is a route to the generation carbocycles that are scaffolds of many

important natural products and biologically active molecules Although the mechanism of

intermoelcular Heck reactions is well established the intramelecular variant is not analyzed in detail

for its mechanistic features Using Density Functional Theory computations we have explored the

the catalytic cycle of intramolecular Heck reaction that involves oxidative addition migratory

insertion (cyclization) and β-hydride elimination (See Figure) Two pathways were analyzed which

differ in their initial coordination face (Re or Si) of the terminal alkene with the metal centre The

choice of pathway is not evident from free energy profile because one of the pathways have higher

barrier for oxidative addition the other requires high activation energy for β-hydride elimination

Detailed analysis of the mechanism will be presented In addition our attempts to analyze such

complex reaction mechanisms by kinetic simulations will be discussed

Figure Catalytic cycle for the intramolecular Heck reaction

73

OC12

CYCLODIMERIZATIONS OF DONOR-ACCEPTOR CYCLOPROPANES

SHORTCUT APPROACH TO COMPLEX RING SYSTEMS

EM Budynina OA Ivanova AO Chagarovskiy IV Trushkov

Moscow State University Department of Chemistry Moscow Russia

Cyclodimerization is among the most challenging and fascinating reactions providing significant

increase in structural complexity within one operation step in highly stereoselective manner and

occurring both in vivo and in vitro In organic synthesis among typical substrates that undergo

cyclodimerizations donor-acceptor (DA) cyclopropanes1 in which small ring is vicinally activated

with donor and acceptor groups occupy a special place Currently at least dozen types of Lewis

acid-triggered cyclodimerization of such DA cyclopropanes as 2-(het)aryl-cyclopropane-11-

diesters are known which open rapid approaches to diverse ring compounds including complex

polycyclic and bridged molecular systems2

Recently on basis of (3+3)-cyclodimerizations of 2-arylcyclopropane-11-diesters we developed

straightforward and efficient approaches to 14-diarylcyclohexanes 1-aryltetralins or 910-

dihydroanthracenes2a

(3+2)-Cyclodimerizations of similar cyclopropanes provide an easy access to

diarylcyclopentanes2bc

and arylindanes2d

Cyclodimerizations of 3- and 4-indolyl-derived DA

cyclopropanes allows for the construction of complex tetra- and heptacyclic cores of bisindoles2e

1 a) Reissig H-U Zimmer R Chem Rev 2003 103 1151 b) De Simone F Waser J

Synthesis 2009 3353 c) Melrsquonikov MYa Budynina EM Ivanova OA Trushkov IV

Mendeleev Commun 2011 21 293 d) Schneider TS Kaschel J Werz DB Ang Chem Int

Ed 2014 53 101002anie201309886

2 a) Ivanova OA Budynina EM Chagarovskiy AO Trushkov IV Melnikov MYa J

Org Chem 2011 76 8852 b) Chagarovskiy AO Ivanova OA Budynina EM Trushkov

IV Melnikov MYa Tetrahedron Lett 2011 52 4421 c) Novikov RA Korolev VA

Timofeev VP Tomilov YuV Tetrahedron Lett 2011 39 4996 d) Ivanova OA Budynina

EM Skvortsov DA Limoge M Bakin AV Chagarovskiy AO Trushkov IV

Melnikov MYa Chem Commun 2013 49 11482 e) Ivanova OA Budynina EM

Chagarovskiy AO Rakhmankulov ER Trushkov IV Semeykin AV Shimanovskii NL

Melnikov MYa Chem Eur J 2011 17 11738 f) Novikov RA Tarasova AV Korolev

VA Timofeev VP Tomilov YuV Ang Chem Int Ed 2014 53 3187 g) Novikov RA

Tomilov YuV Helv Chim Acta 2013 96 2068

74

OC13

USING RING STRAIN RELEASE FOR ALLEVIATION OF

TRANSANNULAR STRAIN SMALL RING-TEMPLATED SYNTHESIS OF

MEDIUM HETEROCYCLES

M Rubin M Rubina A Edwards P Ryabchuk

University of Kansas Department of Chemistry

A highly efficient diastereocenvergent reaction of bromocyclopropanes with various nucleophiles

have been recently developed in our laboratories1-7

This reaction involves a base-assisted

dehydrohalogenation to produce a highly reactive cyclopropene intermediate which undergoes

subsequent nucleophilic addition across the strained C=C bond Different intramolecular modes of

this reaction will be presented Possibilities for assembly of heterocyclic scaffolds with various ring

sizes including enantiomerically pure medium heterocycles will be demonstrated The mechanistic

aspect of this transformation and the means of controlling its diastereoselectivity will be discussed

Br

Nu

R

O

N O HN

O

R

R

Me

O

BaseTHF

18-crown-6 (cat)

t-BuOKTHFKOHTHF

t-BuOK DMSO

Ar Me

O

N

R

O

H

H

8-membered 7-10-membered

8-9-membered

N

Ph

Ph

O

t-BuOK THF

5-membered

O

O

R

R8-membered

O

O

O

Me

NH

HNO

Me

15-memberedt-BuOK DMSO

t-BuOK THF

References

[1] Alnasleh B K Sherrill W M Rubina M Banning J Rubin M J Am Chem Soc 2009

131 6906-6907

[2] Banning J E Prosser A R Rubin M Org Lett 2010 12 1488-1491

[3] Prosser A R Banning J E Rubina M Rubin M Org Lett 2010 12 3968-3971

[4] Banning J E Prosser A R Alnasleh B K Smarker J Rubina M Rubin M J Org

Chem 2011 76 3968-3986

[5] Ryabchuk P Rubina M Xu J Rubin M Org Lett 2012 14 1752-1755

[6] Banning J E Gentillon J Ryabchuk P Prosser A R Rogers A Edwards A Holtzen

A Babkov I A Rubina M Rubin M J Org Chem 2013 78 7601-7616

[7] Ryabchuk P Edwards A Gerasimchuk N Rubina M Rubin M Org Lett 2013 15

6010-6013

75

OC14

THE STRATEGY FOR ATOM ECONOMICAL REDUCTIVE ADDITION

DEOXYGENATION

D Chusov PN Kolesnikov VI Maleev NZ Yagafarov

ANNesmeyanov Institute of Organoelement Compounds of Russian Academy of Sciences

Herein we present the concept of using carbon monoxide for atom economical reductive addition

deoxygenation without external hydrogen source [1] We are utilizing this idea by showing that N-

H and C-H bonds of the reagents could be used as hydrogen source (Fig 1)

Figure 1

References

D Chusov B List Angew Chem Int Ed 2014 53 DOI 101002anie201400059

76

OC15

DINUCLEAR CATALYSIS ACCELERATED METAL-DEPENDENT RING-

OPENING POLYMERIZATION OF LACTIDE

E Kirillov

Universite de Rennes 1 UMR 6226 - CNRS 35042 Rennes France

Multinuclear olefin polymerization catalysts (incorporating several active metal centers in one and

the same molecule) have recently emerged as a distinct and brand new class of molecular catalysts 1

Implicit cooperative behavior2 of two or more metal centers in active species of these systems can

contribute to enhanced performance (with respect to mononuclear analogues) in terms of activity

chain-transfer kinetics and also monomers selectivity in copolymerization reactions

Dinuclear complexes of aluminum and indium with a bis(phenoxy-imine) platform have been

synthesized and used in the polymerization of lactide3a

Kinetic studies demonstrated that the

dialuminum precursor (Scheme 1) provides a more favorable reaction pathway in terms of

activation free energy than that of directly related monoaluminum systems3b

No similar trend was

observed with the corresponding diindium monoindium systems which was attributed to a

dissimilar ROP mechanism Details of the mechanisms and key factors of the dinuclear catalysis

will be discussed

Scheme 1 A dinuclear aluminum system enables a 5-to-10 fold boost in activity when compared to

its monoaluminum analogues

1 Delferro M Marks T J Chem Rev 2011 111 2450

2 Bratko I Goacutemez M Dalton Trans 2013 42 10664

3 (a) Normand M Roisnel T Carpentier J-F Kirillov E Chem Commun 2013 49 11692

(b) Normand M Dorcet V Kirillov E Carpentier J-F Organometallics 2013 32 1694

77

OC16

RECENT METHODOLOGICAL DEVELOPMENTS FOR THE QUANTUM

CHEMICAL STUDY OF COMPLEX SYSTEMS

S Irle

Nagoya University Department of Chemistry Nagoya Japan

The structural complexity of molecular clusters increases with size due to the associated rapidly

growing configuration space Two examples are realized in i) the transition from molecular to bulk

systems and ii) in the simulation of extended biosystems In such systems traditional quantum

chemical approaches of investigations are hampered by the vastly increasing computational cost

even considering ever-growing supercomputer capabilities Computationally inexpensive yet

accurate schemes such as the density-functional tight-binding (DFTB) method [1] and there linear

scaling versions promise here a significant advantage

We have recently engaged in developing novel methodologies for systems with increasing

structural complexity driven by motivation from experimental studies In this presentation we will

review a) the Kick-fragment-based ldquoKick3rdquo conformationally aware approach for studying

molecular [2] and ionic liquid clusters with increasing size and our implementation of the fragment

molecular orbital (FMO) method [3] with DFTB called ldquoFMO-DFTBrdquo in the popular GAMESS-

US quantum chemistry package [4] The computational effort of the method scales nearly linearly

with system size with a negligible pre-factor and allows the efficient massively-parallel quantum

chemical geometry optimization and direct molecular dynamics (MD) simulations of systems

containing several tens of thousands of atoms in particular when fragments consist of units with

less than 50 atoms [5] The method should be particularly useful to predict structures of new

artificial peptides and proteins predict enzymatic reaction pathways estimate free energy

contributions along pathways where large parts or even the entire protein including surrounding

water is treated quantum chemically and to simulate the effects of highly polarizable andor

charged solvents in explicit-solvent MD simulations

Unlike other linear scaling schemes such as divide and conquer approaches (DC) FMO-DFTBs

very design allows the insightful decomposition of interaction energies between ligands and

proteins in terms of electrostatics exchange-repulsion charge transfer dispersion and solvent

screening contributions in a straightforward manner

[1] M Gaus Q Cui M Elstner J Chem Theory Comput 7 931 (2011)

[2] M A Addicoat S Fukuoka A J Page S Irle J Comput Chem 34 2591 (2013)

[3] D G Fedorov T Nagata K Kitaura Phys Chem Chem Phys 14 7562 (2012)

[4] M W Schmidt K K Baldridge J A Boatz S T Elbert M S Gordon J H Jensen S

Koseki N Matsunaga K A Nguyen S Su T L Windus M Dupuis and J A Montgomery

Jr J Comput Chem 1993 14 1347 httpwwwmsgameslabgovgamessindexhtml

[5] Y Nishimoto D G Fedorov S Irle submitted

78

OC17

QUANTUM CHEMICAL MODELING IN STUDIES OF MOLECULAR

MECHANISMS OF ENZYME CATALYSIS

AV Nemukhin

Chemistry Department MV Lomonosov Moscow State University Moscow 199991 Russia NM

Emanuel Institute of Biochemical Physics Russian Academy of Sciences Moscow Russia

Recent results [1-3] of modeling chemical transformations in enzyme active sites using quantum-

based approaches will be discussed We apply quantum mechanicsmolecular mechanics (QMMM)

approaches to compute minimum energy pathways connecting enzyme-substrate and enzyme-

product complexes Appropriate crystal structures from the Protein Data Bank usually serve as a

source of coordinates of heavy atoms to create molecular model systems After in silico

construction of a three-dimensional full-atom model evolution of the model system along carefully

selected reaction coordinates is analyzed

Several examples of such modeling will be presented The complete cycle of chemical

transformations in penicillin acylase a unique enzyme that belongs to the recently discovered

superfamily of N-terminal nucleophile hydrolases with its most specific substrate penicillin G

leading to formation of 6-aminopenicillanic and phenylacetic acids [1] will be presented Keton-

ketal transformations at the active site of matrix metalloproteinases characterized computationally

[2] may be explored to propose specific inhibitors Chemical reactions in photoreceptor proteins

constitute an active field of application of QMMM modeling the case of BLUF domains will be

discussed [3]

Simulation results of guanosine triphposphate hydrolysis (GTP) by small GTPases icluding Ras

protein will be in focus According to newly obtained data the molecular events of the chemical

steps upon GTP hydrolysis include (i) cleavage of the phosphorus (Pγ) -oxygen bond in GTP upon

approach of the properly aligned catalytic water molecule producing GDP (ii) formation of a new

chemical bond between phosphorus and oxygen of water (iii) redistribution of protons between

reacting species leading to inorganic phosphate Pi

References

[1] Grigorenko BL Khrenova MG Nilov DK Nemukhin AV Švedas VK Catalytic Cycle of

Penicillin Acylase from Escherichia coli QMMM Modeling of Chemical Transformations in

the Enzyme Active Site upon Penicillin G Hydrolysis ACS Catal 2014 V 4 P 2521ndash2529

[2] Khrenova MG Nemukhin AV Savitsky AP Computational Characterization of Ketone-

Ketal Transformations at the Active Site of Matrix Metalloproteinases J Phys Chem B 2014

V 118 P 4345-4350

[3] Khrenova MG Nemukhin AV Domratcheva T Photoinduced Electron Transfer Facilitates

Tautomerization of the Conserved Signaling Glutamine Side Chain in BLUF Protein Light

Sensors J Phys Chem B 2013 V 117 P 2369-2377

79

OC18

EXCITED STATES AND MOLECULAR INTERACTIONS IN PROTEINS

AND SOLUTIONS

JH Hasegawa

Catalysis Research Center Hokkaido University Sapporo Japan

Solvatochromism and fluorescent solvatochromism are well-known phenomena and there are rich

accumulations in experimental publications Color tuning in proteins such as human color vision

and fluorescent proteins could be also classified to solvatochromism but with a specific

environment where anisotropic molecular interactions play important roles

We have studied biological color tuning with the SAC-CIMM calculations in which MM

description was adopted for the environmental effect This classical description for the environment

works very well for explaining the color tuning mechanisms

In some cases however environmental electronic structure effect becomes important To

investigate the origin of the QM effect we propose a scheme based on the wave function theory

with a MO localization scheme The role of the environmental electronic effect was analyzed in

terms of amino acidsrsquo orbital delocalizations excitonic interactions excited-state polarization and

dispersion interactions In the presentation we would show some results of pilot applications

80

OC19

CATIONIC GOLD-CATALYZED HETEROANNULATIONS

EV Van Der Eycken

University of Leuven (KU Leuven) Department of Chemistry Leuven Belgium

Gold catalysis is one of the fast growing research topics of modern organic chemistry In this

context gold-catalyzed carbocyclization and heteroannulation strategies have recently attracted

much attention due to the selective and efficient activation of the C-C triple bond towards a wide

range of nucleophiles Moreover the combination of multicomponent reactions with gold catalysis

gives access to complex molecular architectures in few steps as compared to traditional multistep

processes We will comment on our recent findings in this field A concise route to indoloazocines1

via a sequential Ugigold-catalyzed intramolecular hydroarylation2 will be presented A diversity-

oriented approach to spiroindoles via a post-Ugi gold-catalyzed diastereoselective domino

cyclization3 will be described (Scheme) as well as a regioselective approach for the synthesis of

pyrrolopyridinones and pyrroloazepinones employing a gold(I)platinum(II) switch4

N

O R3

H2N

R4

COOHR5

NC+

i) Ugi-4CR

NN

N

R5

O

O R3

(+-)

H

R1

R2

R2

R4

R1ii) cationic gold rt

13 examplesup to 80 yield

References

1 Synthesis of Azocino[54-b]indoles via Au-Catalyzed Intramolecular Alkyne Hydroarylation V

A Peshkov O P Pereshivko E V Van der Eycken Adv Synth Cat 354 2841-2848 2012

2 Concise route to indoloazocines via a sequential Ugigold-catalyzed intramolecular

hydroarylation S G Modha D D Vachhani J Jacobs L Van Meervelt E V Van der

Eycken Chem Commun 48 (52) 6550ndash6552 2012

3 Diversity-Oriented Approach to Spiroindolines Post-Ugi Gold-Catalyzed Diastereoselective

Domino Cyclization S G Modha A Kumar D D Vachhani J Jacobs S K Sharma V S

Parmar L Van Meervelt E V Van der Eycken Angew Chem Int Ed 51 9572-9575 2012

4 Gold(I) and Platinum(II) switch A post-Ugi intramolecular hydroarylation to pyrrolopyridinones

and pyrroloazepinones S G Modha A Kumar D D Vachhani S K Sharma V S Parmar E

V Van der Eycken Chem Comm 48 10916-10918 2012

81

OC20

Pd-SUPPORTED BIMETALLIC COMPOSITIONS FOR

STEREOSELECTIVE LIQUID PHASE SEMI-HYDROGENATION OF

DIPHENYLACETYLENE

IS Mashkovsky1 AV Sergeeva

1 OV Turova

1 MN Vargaftik

2 NYu Kozitsyna

2 AYu

Stakheev1

1 - Zelinsky Institute of Organic Chemistry RAS Moscow Russia

2 - Kurnakov Institute of General and Inorganic Chemistry RAS Moscow Russia

This study was focused on the development of the efficient catalyst for selective semi-

hydrogenation of internal alkene Diphenylacetylene (DPA) was used as a model compound The

catalytic compositions based on Pd-Zn Pd-Co Pd-Ni were investigated The samples were

prepared via two techniques (1) on the basis of palladium acetate heterobimetallic complexes as

precursors and (2) using traditional co-impregnation by individual metal salts It was found that the

systems based on bimetallic acetate complexes exhibited a substantial increase in selectivity to

alkene and cis-isomer formation at high conversion of the parent alkyne (DPA) albeit at the

expense of some decrease in the activity The detailed physicochemical study with TEM-EDS

SEM-EDS EXAFS and IR-spectroscopy reveals that the use of heterobimetallic acetate complex as

a precursor allows us to avoid metallic phase segregation during the reduction treatment of the

catalyst which ensures high homogeneity of bimetallic particles and leads to enhanced selectivity

Financial support was provided by RFBR foundation grants 12-03-31487 13-03-12176

Рис 1 Dependency of selectivity to cis-isomer and alkene on DPA conversion for PdAl2O3

catalyst modified with Co Zn and Ni in liquid phase DPA hydrogenation

Se

lecti

vit

y t

o c

is-i

so

me

r

0

10

20

30

40

50

60

70

80

90

100

70 80 90 100

0

10

20

30

40

50

60

70

80

90

100

70 80 90 100

DPA conversion

093PdAl2O3

093Pd-052ZnAl2O3

093Pd-053NiAl2O3

093Pd-053CoAl2O3

DPA conversion

Se

lecti

vit

y t

o a

lke

ne

H

H

H

H

H

H

+

H

H

H

H

+

093PdAl2O3

093Pd-052ZnAl2O3

093Pd-053NiAl2O3

093Pd-053CoAl2O3

82

OC21

DESIGN OF NANOSTRUCTURES ON THE BASIS OF TWO

PHARMACOPHORIC FRAGMENTS - FULLERENE AND PIPERIDINE

DERIVATIVES

GV Grishina IS Veselov IV Trushkov

M V Lomonosov Moscow State University Department of Chemistry

This communication is described the creation of a new nanobiosystems with high antivirus potential

based on the two pharmacophoric fragments - derivatives of fullerene C60 and piperidine ligands

Design of nanoadditive on the basis of two pharmacophoric fragments - functional derivatives of

trans-34-dihydroxypiperidine and organically modified by fullerene C60 can be a very promising

bioactive substances Such a perspective is related to using first as ligands several trans-34-

dihydroxylated piperidines already demonstrated anti-HIV activity and secondly the uniqueness of

fullerene spheroid significantly reduce the toxicity of biologically active adducts We believed that

binding of two biologically active units in the same system will be very useful and promising

N

YX

COOEtON

Me NY

X

1 X = H Y = OH

2 X = Y = OH

3 X =NHR Y = OH

4

Monoadducts 1-4 have obtained by the Benguel and Prato reactions respectively and have since

received 12 new fullerene adducts based on the derivatives of the trans-34-dihydroxypyridine and

trans-4-amino-3-hydroxypiperidines Isolation and identification of these adducts were made using

column and preparative chromatography on silica gel structure and stereochemistry were

established with the involvement required in each case spectral methods including mass

spectrometry and МАLDI X-ray analysis and 1H

13C NMR The main difficulty in undertake

researches consisted of significant differences reactivity due to high lipophilicity derivatives of

fullerene and high hydrophilicity piperidine ligands To reduce this difference we have modified

both fragments introduction to piperidine ligands andor in the molecule organically modified

fullerenes functions andor linkers which facilitated further obtaining of target adducts For some

samples of adducts managed to get soluble in alcohol salts A very important factor has been the

elucidation of the impact of structural and stereochemical factors on possible synergies in the

adduct investigation Target adducts are a new type of nanostructures for medical chemistry with

great pharmacological potential

83

OC22

CHIRASAC STUDY ON CHIRAL SPECTROSCOPY AND PHOTOBIOLOGY

H Nakatsuji T Miyahara

Quantum Chemistry Research Institute (QCRI) 1-36 Goryo-Oohara Nishikyo-ku Kyoto 615-8245

Japan

Weak interactions of molecules with solvents andor environments are of crucial importance in

material science and biology but rather difficult to investigate quantitatively Circular dichroism

(CD) spectra reflect sensitively the conformational structures of chiral molecules their (weak)

interactions with solvents andor proteins etc The SAC-CI method gives their CD spectra very

reliably From this fact the SAC-CI method is a useful tool to investigate the conformational

geometries of chiral molecules their interactions with environments etc by comparing their

experimental and SAC-CI theoretical CD spectra We initiated a systematic molecular technology

called ChiraSac (Chirality + SAC-CI) project (see Figure 1) by using the SAC-CI code and other

highly reliable and useful codes on ldquoGAUSSIANrdquo suit of programs [1] We have already applied

this project successfully to several topics of chiral spectroscopy and photobiology [2-4] We will

present here conformational dependence of α-Hydroxyphenylacetic Acid and similarities and

differences between RNA and DNA etc as some recent applications of ChiraSac to chiral

spectroscopy and photobiology

References

[1] M J Frisch G W Trucks H B Schlegel G

E Scuseria M A Robb J R Cheeseman G

Scalmani V Barone B Mennucci G A

Petersson et al Gaussian 09 Gaussian Inc

Wallingford CT 2009

[2] Circular Dichroism Spectra of Uridine

Derivatives ChiraSac Study Tomoo

Miyahara Hiroshi Nakatsuji and Takehiko

Wada J Phys Chem A 118 2931-2941

(2014)

[3] Conformational Dependence of the Circular

Dichroism Spectrum of α-Hydroxyphenyl-

acetic Acid A ChiraSac Study Tomoo

Miyahara and Hiroshi Nakatsuji J Phys

Chem A 117 14065- 14074 (2013)

[4] Helical Structure and Circular Dichroism

Spectra of DNA A Theoretical Study T

Miyahara H Nakatsuji and H Sugiyama J

Phys Chem A 117 42-55 (2013)

84

OC23

A DFT ANALYSIS ON THE ELECTRONIC PROPERTIES OF

METHYLAMMONIUM LEAD IODIDE PEROVSKITE

K Yamashita1 G Giorgi

1 J Fujisawa

2 H Segawa

2

1 - Department of Chemical System Engineering The University of Tokyo Japan

2 - Research Center for Advanced Science and Technology The University of TokyoJapan

Methylammonium (MA) lead iodide perovskite (CH3NH3PbI3) plays an important role in light

absorption and carrier transport in efficient organicminusinorganic perovskite solar cells [1] In my talk

the first theoretical estimation of effective masses of photocarriers and the role of MA cation in

CH3NH3PbI3 will be discussed

Spin-polarized DFT calculations have been performed with the generalized gradient approximation

From the charge density of the two-fold degenerate states ((a) and (b)) of CBM and those ((c) and

(d)) of VBM one can see that photogenerated electrons around CBM and holes around VBM exist

separately results related to the ambipolar transport nature of the material Effective masses of

photogenerated electrons and holes are estimated to be me =023m0 and mh = 029m0

respectively including spinminusorbit coupling (SOC) effects This result is consistent with the long-

range ambipolar transport property and with the larger diffusion constant for electrons compared

with that for holes in the perovskite which enable efficient photovoltaic conversion [2]

We also have focused our attention on the MA cation and studied the role it plays in the

electronicoptical features of the perovskite paying attention mainly to the iodide compound [3] A

comparison is performed between the electronic properties of MAPbI3 organic-inorganic perovskite

and those of the purely inorganic CsPbI3

References 1 J Bisquert J Phys Chem Lett 4 2597 (2013)

2 G Giorgi J Fujisawa H Segawa K Yamashita J Phys Chem Lett 4 4213 (2013)

3 G Giorgi J Fujisawa H Segawa K Yamashita J Phys Chem 118 12176 (2014)

85

OC24

A HYBRID MCMD REACTION METHOD WITH RARE EVENT-DRIVING

MECHANISM ATOMISTIC REALIZATION OF 2-CHLOROBUTANE

RACEMIZATION PROCESS IN DMS SOLUTION

M Nagaoka

Graduate School of Information Science Nagoya University Furo-cho Chikusa-ku Nagoya 464-

8601 Japan Core Research for Evolutional Science and Technology (CREST) Japan Science and

Technology Agency (JST) Honmachi Kawaguchi 332-0012 Japan ESICB Kyoto University

Kyodai Katsura Nishikyo-ku Kyoto 615-8520 Japan

We demonstrate a new efficient hybrid MCMD reaction method with a rare event-driving

mechanism as a practical lsquoatomisticrsquo molecular simulation of large-scale chemically reactive

systems (Figure 1) Application of the method to (R)-2-chlorobutane molecules in NN-

dimethylformamide (DMF) molecules starting in the optical pure state (100 ee) was found to

successfully provide such an atomistic state with ~0 ee the expected purity of (R)- to (S)-

enantiomers of the racemic mixture in chemical equilibrium [1]

This hybrid MCMD reaction method is promising for studies of various properties in chemically

reactive systems [2] and their stereochemistry as well

Figure 1 Schematic representation of the hybrid MCMD reaction method The curly curves

represent the molecular dynamical (MD) moves in phase space following the equations of motion

while the straight lines with arrows represent the Monte Carlo (MC) moves (or transitions) of the

system (right figure) whose dynamical moves would be extremely rare events In the left figure the

configurational distribution in equilibrium peq

is proportional to the exponential factor exp[-βU]

where U is the global potential function The right figure shows regional distributions eg preq

exp[-βUr] in region r etc The connecting points of the two kinds of moves (open circles) are

selected according to the criteria for chemical reaction occurrence Note that they do not represent

real connections since these points correspond to almost identical states in configuration space but

not in momentum space and with different configurational gradients Wrrarrs and Wsrarrt are the

transition probabilities from state r to s and from s to t respectively [1]

[1] Masataka Nagaoka Yuichi Suzuki Takuya Okamoto Norio Takenaka Chem Phys Lett 583

80 (2013)

[2] N Takenaka Y Suzuki H Sakai M Nagaoka J Phys Chem C 118 10874 (2014)