11th carla winter school 2018...

11th CaRLa Winter School 2018

Heidelberg

February 18-23, 2018

Final Program

3

Welcome to the 11th CaRLa Winter School

Welcome to the CaRLa Winter School in Heidelberg, presented by CaRLa, our joint research laboratory of BASF and University of Heidelberg! With this event, we will foster the international scientific exchange between established and young researches in the field of homogeneous catalysis. The conference takes place from February 18-23, 2018 at the German-American-Institute downtown Heidelberg, within walking distance to the old town. Our scientific program consists of 1 Keynote Lecture, 8 lectures, 8 teaching sessions and poster presentations. There will be a morning and an afternoon session, whereby unlike at most conferences, only the first part of each session will be a scientific lecture, while the second part has a more educational focus. We provide a prolonged lunch break between the two sessions for individual use or further meetings between the participants, except on Tuesday (February 20), were we will have a lunch together at the conference venue. Every participant will have the opportunity to present his poster during the poster sessions and a light dinner will be provided on Sunday, Monday and Wednesday. Tuesday evening is also for individual use or meeting with other participants. We encourage the scientific exchange between all participants during the week and therefore will leave enough room for discussions and also provide a social event for this purpose (visit of the Kulturbrauerei in the old town of Heidelberg). The conference is fully sponsored by BASF and we will have the opportunity for making an excursion to BASF on Thursday afternoon. If you need any help or have questions on the Winter School and your stay in Heidelberg, please do not hesitate to contact us. We wish you all a stimulating and inspiring stay in Heidelberg at our CaRLa Winter School and let´s have a great time!

Thomas Schaub A. Stephen K. Hashmi

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INDEX

Page

Welcome Message

Index

Program

Lecture Sessions

Poster Abstracts

List of Lecturers

List of Participants

Hotel Map

Map of Lunch Venues

3

4

5

10

27

65

66

70

71

5

Sunday, 02/18/2018

Monday, 02/19/2018

Tuesday, 02/20/2018

Wednesday, 02/21/2018

Thursday, 02/22/2018

Friday, 02/23/2018

09:00 – 10:00

Stefan Bräse:

Metal-catalyzed approaches

for com

plex materials and

biologically active

compounds

Ilan Marek:

Rem

ote Fu

nctionalization

Armido Studer:

Electron-Catalysis

Jürgen Klankermayer:

Catalytic Utilization of Carbon

Dioxide as Renew

able C1

Resource: Catalytic Chess at the

Interfa

ce of E

nergy and Chemistry

Bernd Straub:

Carbene Com

plexes of C

oinage

Metals: Stru

cture, Electronics, and

Hom

ogeneous Catalysis

10:00 – 10:15

Coffee Break

Coffee Break

Coffee Break

Coffee Break

Coffee Break

10:15 – 11:15

11:15 – 11:30

Coffee Break

Coffee Break

Coffee Break

FPP, Lunch and Poster Session

Coffee Break

11:30 – 12:00

Flash Poster Presentation

(FPP)

FPP, BASF Career-Lunch FPP

Poster Prize Ceremony & Closing

Remarks

12:00 – 14:30

13:00 Excursion to BASF

Departure

14:30 – 15:30

Mark Lautens:

Improving Efficiency via

Catalytic and Multicatalytic

Reactions

Mats Tilset:

Small-m

olecule chem

istry

at Au(III)

Didier Bourissou:

Gold catalysis under ligand

control

15:30 – 15:45

Coffee Break

Coffee Break

Coffee Break

15:45 – 16:45

until 16:45 Arrival & Welcome

Coffee

16:45 – 17:00

Opening Ceremony

A. Stephen K. Hashmi

Coffee Break

Coffee Break

Coffee Break

17:00 – 18:00

Martin Ernst:

Alcohol Amination: Needs and

Solutions from

an Industrial

Persepective

(Keynote Lecture BASF)

FPP and Poster Session



18:00 – 22:00

Free Time

Light Dinner

Light Dinner

Mark Lautens:

Devising New

Multicatalytic

Reactions

Mats Tilset:

The importa

nce of trans

effects in the chem

istry of

Au(III)

Didier Bourissou:

Ambiphilic ligands, quo

vadis?

Light Dinner/Get Together

18:00 Symposium Dinner

Jürgen Klankermayer:

Catalytic Utilization of Carbon

Dioxide as Renew

able C1

Resource: Catalytic Chess at the

Interfa

ce of E

nergy and Chemistry

Bernd Straub:

Brainteasers: Counterion

Curiosities and Mechanistic Pitfalls

Free Time (Lunch)

Free Time (Lunch)

Stefan Bräse:

A Retrosynthetic Tour for

Functionalized Materials

Ilan Marek:

1,2-Bisalkylation of Alkenes

Armido Studer:

Catalysis of R

adical

Reactions: A

Radical

Chemistry Perspective

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SUNDAY • 18th February

Until 16:45 Arrival & Welcome Coffee

16:45 Opening Ceremony A. Stephen K. Hashmi

17:00 Keynote Lecture BASF Martin Ernst

18:00 Light Dinner / Get Together

MONDAY • 19th February

09:00 Session Stefan Bräse

10:00 Coffee Break

10:15 Session Stefan Bräse

11:15 Coffee Break

11:30 Flash Poster Presentation (FPP)

12:00 Free Time (Lunch)

14:30 Session Mark Lautens

15:30 Coffee Break

15:45 Session Mark Lautens

16:45 Coffee Break

17:00 Flash Poster Presentation and Poster Session

18:00 Light Dinner

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TUESDAY • 20th February 09:00 Session Ilan Marek

10:00 Coffee Break

10:15 Session Ilan Marek

11:15 Coffee Break

11:30 Flash Poster Presentation, BASF Career-Lunch

14:30 Session Mats Tilset

15:30 Coffee Break

15:45 Session Mats Tilset

16:45 Coffee Break


18:00 Free Time

8

WEDNESDAY • 21th February

09:00 Session Armido Studer

10:00 Coffee Break

10:15 Session Armido Studer

11:15 Coffee Break

11:30 Flash Poster Presentation

12:00 Free Time (Lunch)

14:30 Session Didier Bourissou

15:30 Coffee Break

15:45 Session Didier Bourissou

16:45 Coffee Break


18:00 Light Dinner

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THURSDAY • 22 th February

09:00 Session Jürgen Klankermayer

10:00 Coffee Break

10:15 Session Jürgen Klankermayer

11:15 Flash Poster Presentation, Lunch and Poster Session

13:00 Excursion to BASF

18:00 Symposium Dinner

FRIDAY • 23th February

09:00 Session Bernd Straub

10:00 Coffee Break

10:15 Session Bernd Straub

11:15 Coffee Break

11:30 Poster Prize Ceremony & Closing Remarks

12:00 Departure

10

Lecture Sessions

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1. WO 2011/067200, BASF SE. 2. Ye X.; Plessow P. N.; Brinks M.K.; Schelwies M.; Schaub T.; Rominger F.; Paciello R.; Limbach M.; Hofmann P. J. Am. Chem. Soc. 2014, 136, 5923-5929.

Alcohol Amination: Needs and Solutions from an

Industrial Perspective

Martin Ernst*a

aBASF SE, Carl-Bosch-Str. 38, 67056 Ludwigshafen, Germany

e-mail: [email protected]

Alkyl and specialty amines are important building blocks, process

chemicals and performance chemicals with production volumes in the

range of 3 million metric tons per year. Among the many production

technologies that have been developed over time, the catalytic

amination of alcohols with ammonia to give primary, secondary and

tertiary amines stands out as relatively atom economic and efficient

wherever applicable. BASF SE has been developing the

heterogeneous catalytic alcohol amination for various types of amines

for many years, continuously improving catalytic performance and

process safety by optimizing multimetallic catalyst systems based on

Ni, Co and Cu as main metal components and various supports1.

While mechanistic insights into the heterogeneously catalyzed alcohol

amination remain limited, homogeneous catalysis offers the prospect

of rational design of catalytic systems whose working mechanism is

well understood and tunable2. The aim of the talk is to put these

different technologies into context and evaluate the impact of novel

developments on the industrial production of amines.

12

Metal-catalyzed approaches for complex materials and biologically active compounds

Stefan Bräse*a,b

a Karlsruhe Institute of Technology (KIT), Institute of Organic Chemistry,

Fritz-Haber-Weg 6, 76131 Karlsruhe, Germany

b Institute of Toxicology and Genetics, Hermann-von-Helmholtz-Platz 1,

D-76344 Eggenstein-Leopoldshafen, Germany


In this lecture, we present transition metal-catalyzed approaches towards the synthesis of bioactive natural

product-like structures like steroids1 as well as functionalized

materials, for example functional paracyclophanes.2

1 V. Koch, S. Bräse, Org. Biomol. Chem. 2017, 15, 92-95. Pd-mediated cross-

coupling of C-17 lithiated androst-16-en-3-ol – An access to functionalized

arylated steroid derivatives

2 C. Braun, E. Spuling, N. Heine, M. Cakici, M. Nieger, S. Bräse, Adv. Synth.

Catal. 2016, 1664-1670. Efficient and Modular Synthesis of Isomeric

Mono- and Bis-pyridylparacyclophanes by Cross-Coupling Reactions

13

A Retrosynthetic Tour for Functionalized Materials Nicole Jung,a,b Stefan Bräse*a,b

a Karlsruhe Institute of Technology (KIT), Institute of Organic Chemistry,

Fritz-Haber-Weg 6, 76131 Karlsruhe, Germany

b Institute of Toxicology and Genetics, Hermann-von-Helmholtz-Platz 1,

D-76344 Eggenstein-Leopoldshafen, Germany


The design and synthesis of functionalized organic materials is a pivotal element in modern material sciences. In this course, the participant will get immersed in the modern tools1 of design, retro-synthetic analysis and synthesis of functionalized building blocks for organic electronics.2

1 P. Tremouilhac, A. T. C. Nguyen; Y.-C. Huang, S. Kotov, D. Lütjohann, F.

Hübsch, N. Jung, S. Bräse, J. Chemoinformatics 2017, 9, 54. Chemotion

ELN: An Open Source Electronic Lab Notebook for chemists in academia

14

Improving Efficiency via Catalytic and Multicatalytic Reactions

Mark Lautens*

Department of Chemistry

University of Toronto


In recent years, we have been exploring several concepts designed to improve synthetic efficiency. One is to find new catalytic reactions that result in C-H functionalization. Our focus has been on defining the synthetic utility of the Catellani reaction but we are expanding our studies into several new directions.1 The second theme is to explore the concept of multicatalytic reactions, wherein several catalysts are simultaneously added to a flask to achieve sequential catalytic reactions without interference of one catalyst by the other.2

1 a) Martins, A.; Mariampillai, B.; Lautens, M. “Synthesis in the Key of

Catellani: Norbornene-Mediated ortho C-H Functionalization” Topics in

Current Chemistry 2010, 292, 1-33. b) Ye, J.; Lautens, M. “Palladium

Catalyzed Norbornene-Mediated C-H Functionalization of Arenes” Nature

Chemistry, 2015, 7, 863-870. 2 Panteleev, J.; Zhang, L.; Lautens, M. “Domino Rhodium-Catalyzed Alkyne

Arylation/Palladium Catalyzed N-Arylation: A Mechanistic Approach”

Angewandte Chemie International Edition 2011, 48, 9089-9092.

15

Devising New Multicatalytic Reactions Mark Lautens*

Department of Chemistry

University of Toronto e-mail: [email protected]

In my initial lecture, we explored the concept of multicatalytic reactions, wherein several catalysts are simultaneously added to a flask to achieve sequential catalytic reactions without interference of one catalyst by the other.1,2

This tutorial will ask each participant (or teams) to suggest new multicatalytic reactions and we will discuss the merits and challenges of each. If the innovators agree, we can even consider trying these ideas.

1 Panteleev, J.; Zhang, L.; Lautens, M. “Domino Rhodium-Catalyzed Alkyne

Arylation/Palladium Catalyzed N-Arylation: A Mechanistic Approach”

Angewandte Chemie International Edition 2011, 48, 9089-9092.

2 Yamamoto, K.; Qureshi, Z.; Tsoung, J.; Pisella, G.; Lautens, M.

“Combining Ru-Catalyzed C-H Functionalization with Pd-Catalyzed

Asymmetric Allylic Alkylation: Synthesis of 3-Allyl-3-aryloxindole Derivatives

from Aryl Alpha-Diazoamides“ Organic Letters, 2016, 18, 4954-4957. b)

Yamamoto, K.; Bruun, T.; Kim, J.Y.; Zhang, L.; Lautens, M. “A New

Multicomponent Multicatalyst Reaction (MC)2R: Chemoselective

Cycloaddition and Latent Catalyst Activation for the Synthesis of Fully

Substituted 1,2,3-Triazoles” Organic Letters, 2016, 18, 2644-2647.

16

Remote Functionalization

Ilan Mareka,*

a Schulich Faculty of Chemistry. Technion-Israel Institute of Technology,

Haifa Israel


Combining functionalization at a distant position from a

reactive site with the creation of several consecutive

stereogenic centers, including the formation of a quaternary

carbon stereocentre, in acyclic system represents a pinnacle

in organic synthesis. Here we report the regioselective Heck

arylation of terminal olefins as a distant trigger for the ring-

opening of cyclopropanes. This Pd-catalyzed unfolding of the

strained cycle, driving force of the chain-walking process,

remarkably proved its efficiency and versatility, as the reaction

proceeded regardless of the molecular distance between the

initiation (double bond) and termination (alcohol) sites.

Moreover, employing stereodefined polysubstituted

cyclopropane vaults allowed to access sophisticated

stereoenriched acyclic scaffolds in good yields. Conceptually,

we demonstrated that merging catalytically a chain walking

process with a selective C–C bond cleavage represents a

powerful approach to construct linear skeleton possessing two

stereogenic centers.

17

References for last 3 years contribution, see, a) S. Singh, J. Bruffaerts, A. Vasseur, I. Marek, Nature Com. 2017, 8, 14200; b) Z. Nairoukh, G. GKS Narayana Kumar, Y. Minko, I. Marek, Chem. Sci. 2017, 8, 627; c) S. Raha Roy, H. Eijsberg, J. Bruffaerts, I. Marek, Chem. Sci. 2017, 8, 334; d) D. S. Müller, V. Werner, S. Akyol, H.-G. Schmalz, I. Marek, Org. Lett. 2017, i, 3970; e) P. Stakov, J. T. Moore, D. C. Paquette, B. M. Stoltz, I. Marek, J. Am. Chem. Soc. 2017, 139, 9615; f) F.-G. Zhang, I. Marek, J. Am. Chem. Soc. 2017, 139,8364; g) Z. Nairoukh, M. Cormier, I. Marek, Nature Rev. Chem. 2017, 1, 0035; h) L. Dian, D. S. Müller, I. Marek, Angew. Chem. Int. Ed. 2017, 56, 6783; i) M. Leibelling, K. A. Shurrush, V. Werner, L. Perrin, I. Marek, Angew. Chem. Int. Ed. 2016, 55, 6057; j) S. R. Roy, D. Didier, A. Kleiner, I. Marek, Chem. Sci.2016, 7, 5989; k) F-G. Zhang, G. Eppe, I. Marek Angew. Chem. Int. Ed. 2016,52, 714; l) A. Vasseur, J. Bruffaerts, I. Marek Nature Chem. 2016, 8, 209; m)D. S. Müller, I. Marek J. Am. Chem. Soc. 2015, 137, 15414; n) Z. Nairoukh, I. Marek Angew. Chem. Int. Ed. 2015, 54, 14933; o) R. Vabre, B. Island, C. J. Diehl, P. R. Schreiner, I. Marek Angew. Chem. Int. Ed. 2015, 54, 9996 p) A. Masarwa, D. Gerbig, L. Oskar, A. Loewenstein, H. P. Reisenauer, P. Lesot, P. R. Schreiner, I. Marek Angew. Chem. Int. Ed. 2015, 54, 13106; q) M. Simaan, P.-O. Delaye, M. Shi, I. Marek Angew. Chem. Int. Ed. 2015, 54, 12345; r) A. Vasseur, L. Perrin, O. Eisenstein, I. Marek Chem. Sci. 2015, 6, 277; s) I. Marek, A. Masarwa, P.-O. Delaye, M. Leibeling Angew. Chem. Int. Ed. 2015,54, 414; t) G. Eppe, D. Didier, I. Marek Chem. Rev, 2015, 105, 9175.

18

1,2-Bisalkylation of Alkenes

Ilan Mareka,*

a Schulich Faculty of Chemistry. Technion-Israel Institute of Technology,

Haifa Israel


Although the functionalization of a double bond has been

the focus of intense research in the last few decades (i.e.

hydrocyanation, hydrosilylation hydroboration, hydro-

formylation, diol, epoxides, cyclopropanes, aziridines, amino-

alcohols, etc), the diastereo- and enantioselective bis-

alkylation of non-activated alkene didn’t fulfil his potential yet.

Indeed, the addition of organometallic species to such non-

activated carbon-carbon double bond (carbometalation) would

be an efficient way to create bis-alkylated linear or cyclic

substructures if the new organometallic formed could react

diastereoselectively with various electrophiles.

The challenges and opportunities of this reaction will be discussed.

19

Small-molecule chemistry at Au(III) Marte S.M. Holmsen, Ainara Nova, Sigurd Øien-Ødegaard,

Mats Tilset* Department of Chemistry, University of Oslo, Norway


N Au MeCN

N

H Au

OAcF

N Au OAcF

AcFO OAcF N

H2O O

and O

N

H

Our efficient synthesis of Au(III) complexes with cyclometalated N–C ligands1 facilitated studies of small-molecule reactivity at Au(III). In this contribution, highlights are provided from the ongoing investigation of synthetic and mechanistic studies of alkene reactivity, in particular, at the Au(III) moiety.2

1 Shaw, A.P.; Tilset, M.; Heyn, R.H.; Jakobsen, S.J. Coord. Chem. 2011, 64,

38-47.

2 (a) Langseth, E.; Scheuermann, M.L.; Balcells, D.; Kaminsky, W.; Goldberg,

K.I.; Eisenstein, O.; Heyn, R.H.; Tilset, M. Angew. Chem., Int. Ed. 2013, 52,

1660-1663. (b) Langseth, E.; Nova, A.; Tråseth, E.A.; Rise, F.; Øien, S.; Heyn,

R.H.; Tilset, M. J. Am. Chem. Soc. 2014, 136, 10104-10115. (c) Holmsen,

M.S.M.; Nova, A.; Balcells, D.; Langseth, E.; Øien-Ødegaard, S.; Tråseth, E.A.;

Heyn, R.H.; Tilset, M. Dalton Trans. 2016, 45, 14719-14724.

20

)

The importance of trans effects in the chemistry of Au(III)Marte S.M. Holmsen, Ainara Nova, Sigurd Øien-Ødegaard,



N

cat. Au(tpy)(OAcF 2 Au

H H

AcFO OAcF

CF3COOD

H OAcF

D H (OAcF = CF3COO)

The microwave synthesis of Au(III) complexes with cyclo-metalated N–C ligands1 paved the way to studies of small-molecule (including ethylene2 and acetylene3) reactivity at Au(III). This contribution will probe the importance of trans

effects in the reactivity of Au(tpy)(OAcF)2 and derivatives.


38-47.

2 Langseth, E.; Nova, A.; Tråseth, E.A.; Rise, F.; Øien, S.; Heyn, R.H.; Tilset, M.

J. Am. Chem. Soc. 2014, 136, 10104-10115. (b) Holmsen, M.S.M.; Nova, A.;

Balcells, D.; Langseth, E.; Øien-Ødegaard, S.; Tråseth, E.A.; Heyn, R.H.; Tilset,

M. Dalton Trans. 2016, 45, 14719-14724.

3 Holmsen, M.S.M.; Nova, A.; Balcells, D.; Langseth, E.; Øien-Ødegaard, S.;

Heyn, R.H.; Tilset, M.; Laurenczy, G. ACS Catal. 2017, 7, 5023-5034.

Small-molecule chemistry at Au(III) Marte S.M. Holmsen, Ainara Nova, Sigurd Øien-Ødegaard,



N Au MeCN

N

H Au

OAcF

N Au OAcF

AcFO OAcF N

H2O O

and O

N

H

Our efficient synthesis of Au(III) complexes with cyclometalated N–C ligands1 facilitated studies of small-molecule reactivity at Au(III). In this contribution, highlights are provided from the ongoing investigation of synthetic and mechanistic studies of alkene reactivity, in particular, at the Au(III) moiety.2


38-47.

2 (a) Langseth, E.; Scheuermann, M.L.; Balcells, D.; Kaminsky, W.; Goldberg,

K.I.; Eisenstein, O.; Heyn, R.H.; Tilset, M. Angew. Chem., Int. Ed. 2013, 52,

1660-1663. (b) Langseth, E.; Nova, A.; Tråseth, E.A.; Rise, F.; Øien, S.; Heyn,

R.H.; Tilset, M. J. Am. Chem. Soc. 2014, 136, 10104-10115. (c) Holmsen,

M.S.M.; Nova, A.; Balcells, D.; Langseth, E.; Øien-Ødegaard, S.; Tråseth, E.A.;

Heyn, R.H.; Tilset, M. Dalton Trans. 2016, 45, 14719-14724.

21

Electron-Catalysis

Armido Studer Organic Chemistry Institute, Westfälische Wilhelms University,

Corrensstraße 40, 44149 Münster


In the lecture the concept of using the electron as a catalyst will be discussed.1,2 It will be shown that the electron is an efficient catalyst for conducting various types of radical cascade reactions that proceed via radical and radical ion intermediates. Some recent examples on the use of the electron as a catalyst will be discussed.3

1 A. Studer, D. P. Curran, Angew. Chem. Int. Ed. 2016, 55, 58-102. 2 A. Studer, D. P. Curran, Nature Chem. 2014, 6, 765-773. 3 (a) Zhang, B.; Studer, A. Org. Lett. 2014, 16, 3990-3993. (b) Leifert, D.; Studer, A. Org. Lett. 2015, 17, 386-389. (c) Hartmann, M.; Daniliuc, C. G.; Studer, A. Chem. Commun. 2015, 51, 3121-3123. (d) D. Leifert, D. G. Artiukhin, J. Neugebauer, A. Galstyan, C. A. Strassert, A. Studer, Chem. Commun. 2016, 52,5997-6000. (e) A. Dewanji, C. Mück-Lichtenfeld, A. Studer, Angew. Chem. Int. Ed. 2016, 55, 6749-6752. (f) J. Xuan, C. G. Daniliuc, A. Studer, Org. Lett. 2016,18, 6372–6375. (g) M. Kischkewitz, K. Okamoto, C. Mück-Lichtenfeld, A. Studer, Science 2017, 355, 936-938. (h) X. Tang, A. Studer, Chem. Sci. 2017,DOI: 10.1039/C7SC02175E. (i) T. Hokamp, A. Dewanji, M. Lübbesmeyer, C. Mück-Lichtenfeld, E.-U. Würthwein, A. Studer Angew. Chem. Int. Ed. 2017, 56,DOI: 10.1002/anie.201706534.

22

Catalysis of Radical Reactions: A Radical Chemistry

Perspective

Armido StuderOrganic Chemistry Institute, Westfälische Wilhelms University,

Corrensstraße 40, 44149 Münster


The tutorial deals with general aspects of catalysis in the field of radical chemistry. The perspective of much of the recent work on catalysis in radical reactions is catalysis. The goal of the presentation is to complement this with a radical perspective.1 It is often better to consider reactions by the kind of radical transformation that is occurring rather than by the catalyst that is being used. It will be shown that many reactions in “radical catalysis” have significant innate components; or in other words significant background chain reactions occurring where the catalyst is not involved. Therefore, care has to be taken when discussing catalysis in radical reactions.

1 A. Studer, D. P. Curran, Angew. Chem. Int. Ed. 2016, 55, 58-102.

23

2

Gold catalysis under ligand control

Didier Bourissou*a aLaboratoire Hétérochimie Fondamentale et Appliquée, Université de Toulouse-CNRS, 118 route de Narbonne, 31062 Toulouse, France

e-mail: [email protected]tlse.fr

PR2 NMe

TM reactivity PR2

Au

P Ad Ad

2e redox catalysis

With the aim to open new avenues in catalysis, we have challenged the presumed reluctance of gold to undergo several key elementary transformations. Thanks to rationale ligand design, we have shown that gold complexes can undergo oxidative addition, migratory insertion and β-H elimination

under very mild conditions.1 The specific properties of gold

and the precise role of the “ancillary” ligands will be discussed. Stoichiometric studies and catalytic applications will be presented.

1 Joost, M.;; Amgoune, A.;; Bourissou, D. Angew. Chem. Int. Ed. 2015, 54,

15022-15045.

R2P I

24

Ambiphilic ligands, quo vadis?

Didier Bourissou*a aLaboratoire Hétérochimie Fondamentale et Appliquée, Université de Toulouse-CNRS, 118 route de Narbonne, 31062 Toulouse, France

e-mail: [email protected]tlse.fr

Polyfunctional ligands play a prominent role in coordination chemistry and homogeneous catalysis. This session will deal with ambiphilic ligands, ie ligands combining electron donor

and acceptor sites.1 The following points will be debated based

on selected examples from recent literature:

- Incorporating Lewis acids (LA) moieties in the coordination of transition metals (TM), what for?

- The concept of Z-type σ-acceptor ligands. - Cooperative TM / LA catalysis.

1 a) Amgoune, A.;; Bourissou, D. Chem. Commun. 2011, 47, 859-871;; b)

Bouhadir, G.;; Bourissou, D. Chem. Soc. Rev. 2016, 45, 1065-1079.

25

Catalytic Utilization of Carbon Dioxide as Renewable C1 Resource: Catalytic Chess at the Interface of Energy and

Chemistry

Jürgen Klankermayera,*

a Institut für Technische und Makromolekulare Chemie, RWTH Aachen

University, Worringerweg 2, 52074 Aachen, Germany


The utilization of carbon dioxide (CO2) as a raw material for

chemical synthesis has intrigued chemists ever since it was

recognized that nature capitalizes on this molecule to harness

the energy of the sun for production of organic matter through

photosynthesis. Especially in the last two decades, the

utilization of renewable resources as chemical building block,

solvent, or additive has emerged as important research area for

the development of sustainable chemical processes. In this

respect, CO2 is an important, but challenging renewable C1

resource, which is already used as raw material for the

production of industrial chemicals in certain cases and

intensively researched for novel transformations.1-4

Herein, the challenges and opportunities using CO2 as a C1

synthon in catalytic reactions and processes are presented. The

general aspects will be illustrated with current research from our

laboratories concerning the development, application, and

mechanistic understanding of catalysts and catalytic systems.

[1] J. Klankermayer, W. Leitner, Science, 2015, 350, 629. [2] J. Klankermayer, S. Wesselbaum, K. Beydoun, W. Leitner, Angew. Chem. Int. Ed. 2016, 55, 7296-7343. [3] K. Thenert, K. Beydoun, J. Wiesenthal, W. Leitner, J. Klankermayer, Angew. Chem. Int. Ed. 2016, 55, 12266-12269. [4] B. G. Schieweck, J. Klankermayer, Angew. Chem. Int. Ed. 2017, 56, 10854-10857.

26

Carbene Complexes of Coinage Metals: Structure, Electronics, and Homogeneous Catalysis

Bernd F. Straub*,a

a Organisch-Chemisches Institut, Universität Heidelberg,

Im Neuenheimer Feld 270, D-69120 Heidelberg, Germany


Complexes of copper, silver and gold with reactive carbene ligands are central, yet short-lived, catalytic intermediates of numerous organic-synthetic transformations.1

Dinuclear copper(I) complexes with bis-N-heterocyclic carbene ancillary ligands feature high activity in homogeneous CuAAC “click” catalysis.2

Ar Ar

Ar Ar N N N N [PF6]

H3C

Ar Ar

Ar M

CH3

Ar NTf2

H3C

H3C

N N N

Cu Cu

O O

CH3

N

H3C

CH3

M = Cu, Ag, Au; Ar = C6H4tBu

1 a) Hussong, M. W.; Rominger, F.; Krämer, P.; Straub, B. F. Angew. Chem. Int.

Ed. 2014, 53, 9372-9375; b) Hussong, M. W.; Hoffmeister, W. T.; Rominger, F.;

Straub, B. F. Angew. Chem. Int. Ed. 2015, 54, 10331-10335.

2 Makarem, A.; Berg, R., Rominger, F.; Straub, B. F. Angew. Chem. 2015, 127,

7539-7543; Angew. Chem. Int. Ed. 2015, 54, 7431-7435.

27

Poster Abstracts

28

Poster 1

CaRLa – The Catalysis Research Laboratory

A. Stephen K. Hashmi*a,b and Thomas Schaub*a,c aCatalysis Research Laboratory, Im Neuenheimer Feld 584, D-69120

Heidelberg. bOCI, Universität Heidelberg, Im Neuenheimer Feld 270, D-69120

Heidelberg. cBASF SE, Synthesis and Homogeneous Catalysis,

D-67056 Ludwigshafen.

e-mail: [email protected], [email protected]

CaRLa aims to build up an efficient network between academia and industry to facilitate transfer of knowledge between both partners (University of Heidelberg and BASF SE) and to develop new homogeneous catalysts with application potential within industry. In CaRLa research projects are initiated and funded by BASF as well as by the University of Heidelberg. In these projects, we work in close collaboration and tight exchange between BASF and the University of Heidelberg. In our projects, we focus on problems in homogeneous catalysis with industrial relevance, where also examples from academia are rare. Our projects require a deep mechanistic understanding for a rational development of new catalytic systems, whereby the transfer to an application or to a further process development is the goal of each CaRLa-project.

29

Poster 2

Towards the Total Synthesis of Belizentrin Felix Anderl, Sylvester Größl, Alois Fürstner

Max Planck Institut für Kohlenforschung


Our interest in the total synthesis of biologically active natural products led us to embark on a program towards the synthesis of the marine natural product belizentrin. 1 In addition to its pronounced (neuro-)toxicity, the target has intriguing structural features and synthetic challenges. Here we present our progress to a late stage intermediate en route to belizentrin.

1 Domínguez, H. J.; Napolitano, J. G.; Fernandez-Sanchez, M. T.;

Cabrera-García, D.; Novelli, A.; Norte, M.; Fernandez, J. J.; Hernandez

Daranas, A.; Org. Lett. 2014, 16, 4546-4549.

30

Highly Active Dinuclear Copper Catalysts for the Azide-Alkyne Cycloaddition

Regina Berg,a Oliver Trapp,a Bernd F. Straub*b

aDepartment Chemie, Ludwig-Maximilians-Universität München.bOrganisch-Chemisches Institut, Universität Heidelberg.


The copper-catalyzed azide-alkyne cycloaddition (CuAAC)1 is a variant of Huisgen’s 1,3-dipolar cycloaddition2 which disbur-dens the thermal reaction from its major drawbacks such as poor regioselectivity. In contrast to the widely used “black box” reagent mixtures, a molecularly defined catalyst system for ho-mogeneous CuAAC has been developed.3 Based on the pos-tulated stepwise mechanism, its most important structural fea-ture is the presence of two Cu(I) ions in the same catalyst mo-lecule. A modular synthesis for bistriazolium salt precursors for the ligand system was devised, and reaction with Cu(I) acetate furnished catalytically active dinuclear Cu(I) complexes.

1 Huisgen, R. Proc. Chem. Soc. 1961, 357–396; 2 Rostovtsev, V. V.; Green, L.

G.; Fokin, V. V.; Sharpless, K. B. Angew. Chem. Int. Ed. 2002, 41, 2596–2599; 3 Berg, R.; Straub, J.; Schreiner, E.; Mader, S.; Rominger, F.; Straub, B. F.

Adv. Synth. Catal. 2012, 354, 3445–3450.

Poster 3

31

Iodine-Catalysed C-H Amination Alexandra E. Bosnidou,a Kilian Muñiz*a

a Institute of Chemical Research of Catalonia (ICIQ),

Av. Països Catalans 16, 43007 Tarragona, Spain


The direct C-H amination of hydrocarbons is an issue of paramount importance as it allows for a versatile instalment of the important C-N function. It has received manifold attention from the synthetic community, and transition metal-catalysed processes have been at the centre of attention.1 An interesting economically and ecologically viable alternative to these pathways includes the use of mild iodine(III) reagents. Herein, we report the combination of these reagents with catalytic amounts of molecular iodine for the unparalleled construction of C-N bond from simple hydrocarbon entities. The common step in the catalytic synthesis of pyrrolidines as well as substituted arylamines is based on a light-initiated formation of a nitrogen centred radical, which promotes selective C-H-functionalisation via defined hydrogen atom abstraction.2,3 1 Park, Y.;; Kim, Y.;; Chang, S. Chem. Rev. 2017, 117, 9247-9301. 2 (a) Martínez, C.;; Muñiz, K. Angew. Chem. Int. Ed. 2015, 54, 8287-8291. (b)

Martínez, C.;; Bosnidou, A. E.;; Allmendinger, S.;; Muñiz, K. Chem. Eur. J. 2016,

22, 9929-9932. 3 Bosnidou, A. E.;; Muñiz, K. Manuscript in preparation.

Poster 4

32

Catalytic activity of carbohydrate-functionalised transition metal–NHC systems

Joseph Byrne,a Martin Albrecht *a

aDepartment of Chemistry and Biochemistry, University of Bern, Freiestrasse 3,

3012 Bern, Switzerland


N-Heterocyclic carbenes (NHC) are versatile ligands in various catalytic systems1. Facile preparation of 1,2,3-triazolylidenesthrough ‘click’ chemistry makes these ligands particularlyattractive. We report transition metal–NHC complexes with incorporated carbohydrate functionality, introducing inherent stereochemistry and function to the systems. Use of carbohydrates as phosphine and phosphinite ligand scaffolds has shown promise in asymmetric catalysis.2 Similar work with NHCs is scarce.3 Combining these two important classes of compound into a hybrid system will give rise to synergistic advantages. Catalytic activity of these complexes is presented.

1Mercs, L.; Albrecht, M., Chem. Soc. Rev. 2010, 39, 1903; Melaimi, M.;

Soleilhavoup, M.; Bertrand, G.; Angew. Chem. Int. Ed. 2010, 49, 8810.2Woodward, S.; Dieguez, M.; Pamieez, O.; Coord. Chem. Rev. 2010, 254, 20073For example: A. S. Henderson, J. F. Bower, and M. C. Galen, Org. Biomol.

Chem. 12 (2014) 9180; Pretorius, R.; Olguín, J.; Albrecht, M.; Inorg. Chem.

2017, 56, 12410.

Poster 5

33

Poster 6

Applications of CO2 functionalisation

Alban Cadu,a Saumya Dabral,a Nicolas Germain,a

Simone Manzini,a Oliver Trapp,aThomas Schauba,b* a CaRLa – Catalysis Research Laboratory, INF 584, D-69120 Heidelberg, b BASF SE, Synthesis & Homogeneous Catalysis, Carl-Bosch-Straße 38,

D-67056 Ludwigshafen, Germany,

e-mail: [email protected] Phosgene-free Synthesis of Isocyanates using CO2 and

Organotin(IV) Alkoxides1

Isocyanates are used to form polyurethanes (valuable polymers). The reaction between an amine and CO2 leads to

a transient carbamic acid which can be trapped in situ by an alcohol provided by dialkyltin(IV) alkoxides, subsequent cleavage leads to the desired isocyanate and alcohol. This avoids the formation of HCl of the phosgene method. Sodium Acrylate from Ethylene and CO2

2

The one-pot synthesis of sodium acrylate through catalytic carboxylation of ethylene with CO2 in the presence of a base

is a reaction of high interest. This dream reaction was achieved with non-toxic solvents, re-generable base, catalyst recycling and easy product separation.

1 N. Germain, M. Hermsen, T. Schaub, O. Trapp, Appl. Organomet. Chem., 2017, DOI: 10.1002/aoc.3733 2 S. Manzini, A. Cadu, A.-C. Schmidt, N. Huguet, O. Trapp, R. Paciello, T. Schaub, ChemCatChem. 2017, 9, 2769-2774.

34

Ruthenium-Catalyzed Deaminative Hydrogenation of

Nitriles to Primary Alcohols

Pilar Calleja,a István G Molnár,a Martin Ernst,b

A. Stephen K. Hashmi,a,c Thomas Schaub *a,b

aCaRLa – Catalysis Research Laboratory, Heidelberg, Germany.bBASF SE, Synthesis & Homogeneous Catalysis, Ludwigshafen, Germany.

cOrganisch-Chemisches Institut, Ruprecht-Karls-Universität Heidelberg,

Heidelberg, Germany.


The deaminative hydrogenation of nitriles towards alcohols is a useful reaction to transform nitriles into alcohols with NH3 as the sole by-product. 1 Using the simple and robust RuHCl(CO)(PPh3)3 as the catalyst, at low H2 pressures a series of aliphatic and aromatic nitriles can be transformed into the corresponding alcohols. Suitable solvent systems for these reactions are 1,4-dioxane/water or EtOH/water mixtures. In most cases the selectivity for the alcohols is excellent and the corresponding amines are formed only in trace amounts.

1 Molnár, I. G.; Calleja, P.; Ernst, M.; Hashmi, A. S. K.; Schaub, T.

ChemCatChem. 2017, 9, 4175-4178.

Poster 7

35

Manganese-catalyzed benzylic C(sp3)—H amination for late-stage functionalization

Joseph R. Clark, Kaibo Feng, Anasheh Sookezian and M. Christina White

Roger Adams Laboratory, Department of Chemistry, University of Illinois,

Urbana, Illinois 61801, United States


While selective intramolecular C—H amination reactions are known, intermolecular C—H amination reactions with high reactivity and selectivity are scarce. Achieving high levels of reactivity while maintaining excellent site-selectivity and functional group tolerance remains a frontier challenge for intermolecular C—H amination. We report a novel manganese perchlorophthalocyanine catalyst [Mn(ClPc)] for a highly site-selective intermolecular benzylic C—H amination of bioactive molecules and natural products. In the presence of Brønsted or Lewis acid, the [Mn(ClPc)]-catalyzed C—H amination demonstrates unprecedented tolerance for 3˚ amine, pyridine, and benzimidazole functionalities.1 Contrary to analogous C—H amination systems, mechanistic studies suggest that C—H cleavage is the rate-determining step of the reaction. 1Clark, J. R.;; Feng, K.;; Sookezian, A.;; White, M. C. Nat. Chem. Accepted in

principle

Poster 8

36

Poster 9

Sustainable Catalytic Design based on Cobalt Pincer Complexes

Prosenjit Daw, Subrata Chakraborty, Jai Anand Garg, David

Milstein Department of Organic Chemistry, Weizmann Institute of Institution

Rehovot, Israel, 761001; e-mail: [email protected]

In terms of sustainability, a one-step, atom-economical

efficient methodology to synthesize value-added products from

renewable resources is highly desirable. Owing to economic

constraints, limited availability and toxicity issues, the

replacement of expensive noble-metal catalysts by

environmentally benign earth-abundant base metal catalysts is

of much current interest in homogeneous catalysis.

Acceptorless dehydrogenative coupling of 1,4-substituted- 1,4-

butanediols and various amines using a Co-PNNH pincer

complex to generate 1,2,5-substituted pyrroles liberating water

and dihydrogen as the only by-products was explored (Figure

1)1. In another process, a green route for the N-formylation of

amines by the use of a mixture of CO2 and H2 as a formylating

agent is also described (Figure 1)2. CO2 is a non-toxic and

hydrogen gas is the cleanest and most atom-economical

reducing agent. A wide range of amines were converted to

their corresponding formamides under CO2 and H2 pressure

catalyzed by a Co-PNP pincer complex.

37

Figure 1 Dehydrogenation and Hydrogenation reactions using cobalt pincer complexes. [1] Daw, P.; Chakraborty, S.; Garg, J. A.; Ben-David, Y. and Milstein, D. Angew. Chem. Int. Ed. 2016, 55, 14373–14377. [2] Daw, P.; Chakraborty, S.; Leitus, G.; Diskin-Posner, Y.; Ben-David, Y.; and Milstein, D. ACS Catal. 2017, 7, 2500−2504.

38

A Highly-Developed Phosphine Ligand Facilitates Pd-Catalyzed C–N Coupling in the Presence of

Weak Amine Bases Joseph M. Dennis,a Nicholas A. White,a Richard Y. Liu,a Stephen L. Buchwald*a

aDepartment of Chemistry, Massachusetts Institute of Technology, Cambridge,

Massachusetts 02139, United States


Through use of a sterically demanding dialkyltriaryl monophosphine ligand (AlPhos), the palladium-catalyzed coupling of aryl (pseudo)halides with aryl amines, amides, and aliphatic amines was performed in the presence of weak, soluble organic bases. The mild conditions permit base-sensitive functional groups that were not tolerated with previous methods. Kinetic data, 31P NMR studies, and crystallographic analyses of isolated reaction intermediates have shown that the reaction mechanism changes for different substrate classes. 15N NMR studies of amine-bound palladium complexes provide evidence that the size of alkyl groups on the ligand affect the charge of the Pd atom, which is thought to influence the N–H acidity of Pd-bound amines.

Poster 10

39

1 W. Nam, Acc. Chem. Res., 48, 2415-2423 (2015). 2 E. I. Solomon, T. C. Brunold, M. I. Davis, J. N. Kemsley, S.-K. Lee, N. Lehnert, F. Neese, A. J. Skulan, Y.-S. Yang, J. Zhou, Chem. Rev., 100, 235-350 (2000). 3 C. Krebs, D. G. Fujimori, C. T. Walsh, J. M. Jr. Bollinger, Acc. Chem. Res., 40, 484-492 (2007). 4 C. A. Grapperhaus, B. Mienert, E. Bill, T. Weyhermüller, K. Wieghardt, Inorg. Chem., 39, 5306-5317 (2000). 5 P. Comba, S. Wunderlich, Chem. Eur. J., 16, 7293–7299 (2010). 6 O. Planas, M. Clémancey, J.-M. Latour, A. Company, M. Costas, Chem. Commun., 50, 10887-10890 (2014).

A bispidine iron(IV)-oxo complex for selective halogenation

Dieter Faltermeiera, Katharina Blehera, Saskia Kriega, Peter Combaa,b

aHeidelberg University, Institute for Inorganic Chemistry, INF 270, bInterdisciplinary Center for Scientific Computing (IWR), INF 205, 69120 Heidelberg, Germany;; e-mail: [email protected]heidelberg.de,

[email protected]heidelberg.de

Mononuclear non-heme iron enzymes play an important role in nature.

They occur in many organisms and exhibit a remarkable chemical

versatility. Examples of reactions with non-heme iron compounds

include hydroxylation, halogenation and epoxidation of alkane and

alkene substrates. To understand enzymatic non-heme iron reactions,

the study of biomimetic iron-oxo complexes is important.1-4 Here we

present a high-spin iron(IV)oxo complex,5 which selectively

halogenates alkanes. Hence, this complex is an interesting synthetic

model for non-heme iron halogenase enzymes. The evidence of an

iron(IV)-oxo active site is shown via sulfoxidation (oxygen atom

transfer) and mass spectrometry, while the reaction mechanism is

investigated with DFT calculations (def2-TZVP/B3LYP level of theory

and PCM solvent model) and product analyses under various

conditions to explain the selectivity of halogenation vs. hydroxylation.

Moreover, a comparison is made between our model system that leads

to selective halogenation and an iron(IV)-oxo complex6 that leads to

selective hydroxylation.

Poster 11

40

Poster 12

Electronic ligand effects on the photochemistry of novel [Cu(P^P)(dmphen)]BF4 complexes

Paola Andrea Forero Cortes,a,b Chenfei Li,a David B. Cordes,a Alexandra M. Z. Slawin,a Esteban Mejía b Eli Zysman-Colman,*a

and Paul Kamer*b aUniversity of St Andrews, bLeibniz Institute for Catalysis - LIKAT

e-mail: eli.zysman-colman@st-andrews.ac.uk,[email protected]

The application of the p-aryl-substituted xantphos derivatives in the photoredox Cross-Dehydrogenative Coupling of tetrahydroisoquino-

line with nitromethane1 allowed us to correlate the photophysical properties of a Hammett series of [Cu(P^P)(dmphen)]BF4 photo-catalysts with reactivity (Figure 1).

Figure 1. CDC of tetrahydroisoquinoline with nitromethane

1. Wang, B.;; Shelar, D.;; Han, X.;;Li, T.;; Guan, X.;; Lu, W.;; Liu, K.;; Chen, Y.;; Fu, W.;; Che, C, Chem. Eur. J. 2015, 21, 1184-1190.

41

Dicopper Complexes for CuAAC “Click” Catalysis

Florian Heinricha, Andreas Zech,a Anne Schöffler,a Frank Rominger, Bernd F. Straub*a

a Organisch-Chemisches Institut, Universität Heidelberg, Im Neuenheimer Feld

270, D-69120 Heidelberg, Germany

e-mail: [email protected]heidelberg.de

The copper-catalyzed azide-alkyne cycloaddition (CuAAC) is a prime example for a “click” reaction. 1 Dinuclear copper(I) complexes of bis-N-heterocyclic carbene ancillary ligands feature outstanding catalytic activity. 2 We develop straight-forward syntheses for new, e.g. water-soluble NHC ligands and their molecularly defined dicopper acetate complexes.

1 Berg, R., Straub, B. F. Beilstein J. Org. Chem. 2013, 9, 2715-2750. 2 a) Makarem, A.;; Berg, R., Rominger, F.;; Straub, B. F. Angew. Chem. 2015,

127, 7539-7543;; Angew. Chem. Int. Ed. 2015, 54, 7431-7435;; b) Berg, R.,

Straub, J.;; Schreiner, E.;; Mader, S.;; Rominger, F.;; Straub, B. F. Adv. Synth.

Catal. 2012, 354, 3445-3450;; c) Schöffler, A.;; Makarem, A.;; Rominger, F.;;

Straub, B. F. Beilstein J. Org. Chem. 2016, 12, 1566-1572.

Poster 13

42

Poster 14

Computational Study of the Chromium-Catalyzed

Decomposition of Alkyl Hydroperoxides to Ketones

Marko Hermsen,a,b Jessica Hamann,a Anna-Corina Schmidt,a

Ansgar Schäfer,b Peter Comba,c Thomas Schauba,d

aCatalysis Research Laboratory (CaRLa), INF 584, Heidelberg, Germany.

bBASF SE, Quantum Chemistry & Molecular Simulation, Carl-Bosch-Str. 38,

Ludwigshafen, Germany. cInstitute for Inorganic Chemistry & IWR at

Heidelberg University, INF 270, Heidelberg, Germany. dBASF SE, Synthesis &

Homogeneous Catalysis, Carl-Bosch-Str. 38, Ludwigshafen, Germany.


Chromium(VI) compounds were identified as promising candidates for the decomposition of cyclohexyl hydroperoxides to cyclohexanone and water. As current industrial decomposition catalysts also forms the corresponding alcohol, we set out to explain the formation of ketone in a radical-free mechanism. The insight gained will be of interest for development of ketone-selective decomposition catalysts. This poster will focus on the computational investigation of different possible mechanisms and the identification of an intramolecular hydrogen transfer that is key to the observed reactivity.1 1 Schmidt. A.-C.; Hermsen M.; Rominger F.; Dehn F.; Teles J. H.; Schäfer A.;

Trapp O.; Schaub T. Inorg. Chem. 2017, 56 (3), 1319.

43

Poster 15

Chromium-catalyzed Dehydroperoxidation of Alkyl hydroperoxides

J. N. Hamann,a M. Hermsen,a A.-C. Schmidt,a J. H. Teles,b R. Paciello,b A. S. K. Hashmi,c T. Schauba,b

aCatalysis Research Laboratory Heidelberg (CaRLa), INF 584, Heidelberg,

Germany. bBASF SE, Synthesis & Homogeneous Catalysis,

Carl-Bosch-Straße 38, Ludwigshafen, Germany. cInstitute of Organic

Chemistry, Ruprecht-Karls-University Heidelberg, INF 270, Heidelberg,

Germany.


Known homogeneous and heterogeneous chromium(VI) catalyst systems were investigated with respect to the favored formation of cyclohexanone during the decomposition of cyclohexyl hydroperoxide (CHHP). The focus was on mechanistic studies using different spectroscopic methods. As in previous decomposition studies, a mechanism via the formation of a metal alkylperoxido intermediate is probable. In situ spectroscopic studies revealed that in case of both the soluble and insoluble catalyst, the selective decomposition happens via a non-radical, non-redox mechanism at the Cr(VI) stage through the formation of a cyclohexylperoxy- chromium(VI) complex.

44

1 P. C. J. Kamer, P. W. N. M. van Leeuwen, Phosphorus(III) Ligands in Homogeneous Catalysis: Design and Synthesis, John Wiley & Sons, Chichester, 2012.

2 Y. Huang, Y. Li, P. H. Leung, T. Hayashi, J. Am. Chem. Soc. 2014, 136, 4865–4868.

3 M. Dieckmann, Y. Jang, N. Cramer, Angew. Chem. Int. Ed. 2015, 54, 12149–12152.

4 Y. Jang, M. Dieckmann, N. Cramer, Angew. Chem. Int. Ed. 2017, 56, 15088–15092.

Cooperative Effects between Chiral CpxIrIII Catalysts and Chiral Carboxylic Acids in Enantioselective C-H

Amidations of Phosphine Oxides Yun-Suk Jang, a Michael Dieckmann, a and Nicolai Cramer *a

aLaboratory of Asymmetric Catalysis and Synthesis EPF Lausanne,

Lausanne, CH-1015, Switzerland


Organophosphorus compounds with P-stereogenic centers are valuable motifs in organocatalysts and ligands.1 Only a limited number of catalytic enantioselective approaches have been developed to access molecules with a P-stereogenic center.2 We report that our recently developed chiral CpXIr(III) complex,3 in combination with a chiral carboxylic acid, provides a highly selective C-H amidation process.4 A very strong cooperative effect between the chiral CpXIr(III) complex and the carboxylic acid was discovered. This proved to be pivotal for high enantioselectivities and yields.

Poster 16

45

New Iron(II) Hydrido Complexes and their ReactivityPaul Klaering,*a Mary Grellier,*a Sylviane Sabo-Etiennea

aLaboratoire de Chimie de Coordination, CNRS

205 route de Narbonne, BP 44099, F-31077 Toulouse Cedex 4, France


Recently, first row metals gained major interest for application in homogeneous catalysis, due to their high abundance and

lower costs.1 The presence of hydrosilane moieties (Si−H) in the coordination sphere of those metals might provide access to alternative reaction pathways in selective catalytic trans-formations, such as for instance hydrogenation, hydrosilylation or hydroboration reactions.2,3

In our work, we focus on the synthesis of functionalized hydro-silanes as potential ligand precursors and their coordination at "Fe(PMe3)4".4 Additionally, we present the characterization of the resulting iron(II) hydrido silyl complexes and preliminary reactivity studies with regards to possible catalytic applications.

1 Acc. Chem. Rev. 2015, 48, Special Issue: Earth Abundant Metals …2 Corey, J.Y. Chem. Rev. 2016, 116, 11291-11435.3 Perutz, R.N.; Sabo-Etienne, S. Angew. Chem. 2007, 119, 2630-2645.4 Karsch, H.H.; Klein, H.-F.; Schmidbaur, H. Angew. Chem. 1975, 87, 630-631.

Poster 17

46

Catalysis – A powerful tool for the modification of androsterone as part of the synthesis of Calotropin

Vanessa Koch,a Stefan Bräse*a

a Institute of Organic Chemistry, Karlsruhe Institute of Technology,

Fritz-Haber-Weg 6, 76131 Karlsruhe, Germany e-mail: [email protected], [email protected]

Natural products serve as inspiration for the development of catalytic methods for highly functionalized systems. An important class of natural products are steroids which are widely used substrates to demonstrate the applicability of a developed reaction. But also the synthesis of natural products themselves requires homogenous catalyzed reactions which is shown by the example of Calotropin. It represents a highly functionalized cardenolide with interesting structural motifs like a 1,2-trans-diol and a butenolide moiety. The importance of catalysis in natural product synthesis is demonstrated with a strong accentuation of different types of palladium-catalyzed C–C cross coupling reactions in order to introduce the butenolide ring and further substituents.1,2 Also, a consecutive sequence of metal- and then enzyme-catalyzed reaction play a major role for semi-synthesis of Calotropin.3 1, 2 V. Koch, S. Bräse, Org. Biomol. Chem., 2017,15, 92-95;; V. Koch, M. Nieger,

S. Bräse, Adv. Synth. Catal. 2017, 359, 832-840. 3 Unpublished results

Poster 18

47

Salt-Free Strategy for the Insertion of CO2 into C,H-Bonds: Catalytic Hydroxymethylation of Alkynes Thilo Krause,a Timo Wendling,a Eugen Risto,b

Lukas J. Gooßen*a

aFakultät für Chemie und Biochemie, Ruhr Universität Bochum (Germany) bFachbereich Chemie, TU Kaiserslautern (Germany)


Transformations for the chemical valorization of carbon dioxide as a C1-building block are highly sought-after. Many recent strategies struggle with the generation of tremendous amounts of salt waste, leaving the sustainability aspect of the overall process questionable. In this work, 1 a catalytic system is disclosed that mediates the insertion of carbon dioxide into alkyne C–H bonds using so mild a base that hydrogenation of the resulting carboxylate salt with regeneration of the base becomes thermodynamically feasible. With a simple Cu(I) catalyst and an amine as the base, terminal alkynes readily undergo carboxylation. After an intermediary filtration, the ammonium alkynoate can be hydrogenated to the saturated primary alcohol and water at a rhodium/molybdenum catalyst, regenerating the amine base. This demonstrates the feasibility of an overall salt-free process in which CO2 serves as a C1 building block in a C–H functionalization. 1 T. Wendling, E. Risto, T. Krause, L. J. Gooßen, submitted.

Poster 19

48

Strategies Toward Remote C(sp3)‒H Functionalization of Aliphatic Amines

Melissa Lee,a Pablo J. Cabrera,a Melanie S. Sanford,*a

aDepartment of Chemistry, University of Michigan, Ann Arbor, MI


Amines are an important functional group present in a variety of biologically relevant molecules;; 1 however, remote C–H functionalization of unprotected amines remains challenging. This poster will cover catalytic strategies we have developed to perform selective, remote C(sp3)–H functionalization of aliphatic amines. We have employed protonation as a strategy to deactivate the C–H bonds proximal to nitrogen and enable the platinum-catalyzed, terminal-selective functionalization of aliphatic amines. 2 In addition, we have developed a palladium-catalyzed, directed method that takes advantage of the basic nitrogen atom to enable transannular C–H functionalization of biologically relevant cyclic amine scaffolds.3 1 Vitaku, E;; Smith, D.T.;; Njardarson, J.T. J. Med. Chem. 2014, 57 10257. 2 Lee, M.;; Sanford, M.S. J. Am. Chem. Soc. 2015, 137, 12796. 3 Cabrera, P.J.;; Lee, M.;; Sanford, M.S. Manuscript in Preparation

Poster 20

49

Dehydrogenative Coupling of 4-Substituted Pyridines Utilizing an PNP-Stabilized Zirconium(II) Synthon

Lukas S. Merz,a Hubert Wadepohl,a Eric Clot*b, Lutz H. Gade*a

aInstitute of Inorg. Chem., Ruprecht-Karls-Universität Heidelberg (Germany)bInstitut Charles Gerhardt Montpellier, Université de Montpellier (France)


Despite recent advances in the arylation of N-heteroaromatic compounds, the reductive coupling of two heteroaromatic compounds – particularly to substituted bipyridines – has remained a challenge. In this context, we present the ZrII

synthon, [(cbzPNP)Zr(η6-tol)Cl], which shows a remarkable reactivity towards pyridine substrates.1 Pyridine derivatives with electron withdrawing substituents (R = CF3, CN, F) show no reactivity, while electron donating groups (R’ = OMe, NMe2)lead to C-H activation under formation of η2-pyridyl moieties. On the contrary, para-substituted pyridines (R = H, D, Me, Et, tBu, CH2Ph, CHCHPh) are reductively coupled to the corresponding dianionic 2,2’-bipyridine ligands.

NZrN

tBu

tBu

P

P

Cl

iPr2

iPr2

N

NZrNtBu

tBu

P

P

Cl

iPr2

iPr2

R

RN

R

N

R'

[ZrII]

R'

[(cbzPNP)Zr(Rbipy)Cl][(cbzPNP)Zr(η2-R'py)Cl]

1G. T. Plundrich, H. Wadepohl, E. Clot, L. H. Gade, Chem. Eur. J. 2016, 22,

9283–9292.

Poster 21

50

Reduction of O2 via a Co(IV) Oxyl Radical Complex Supported by a Dianionic Pentadentate Ligand

Lucie Nurdin,a Denis M. Spasyuk,a Laura Fairburn,a Warren E. Piers,*a Laurent Maronb

aDepartment of Chemistry, University of Calgary, Calgary, Alberta, Canada bLPCNO, Université de Toulouse, INSA, UPC, Toulouse, France


Many proteins and enzymes such as cytochrome c oxidase1 and hemoglobin2 are capable of binding O2 via the intermediacy of active sites featuring first row transition metals. Scientists have been devoted to the synthesis and study of these actives sites to gain knowledge about their underlying mechanisms and to develop homogeneous metal-based oxidation catalysts. In this search, we report the reactivity of a Co(II) complex supported by a tetrapodal dianionic ligand3,4 with O2 and propose a detailed mechanistic study based on DFT calculations and experimental data for the reduction of O2 to H2O. This study supports the formation of a highly reactive Co(IV)-oxyl complex and provide fundamental understanding of the O-O breaking mechanism. 1Verkhovsky, M. I.;; Morgan, J. E.;; Wikstroem, M. Biochemistry.1994, 33,

3079-3086. 2Traylor, T. G.;; Berzinis, A. P. PNAS. 1980, 77, 3171-3175. 3Spasyuk, D. M.;; Carpenter, S. H.;; Kefalidis, C. E.;; Piers, W. E.;; Neigid, M. L.;;

Maron, L. Chem. Sci. 2016, 7, 5939-5944. 4Nurdin, L., Spasyuk, D. M., Piers,

W. E.;; Maron, L. Inorg. Chem. 2017, 56, 4157-4168.

Poster 22

51

Introducing the imidazolin-2-iminato chemistry to late transition metals

Marius Peters,a Matthias Tamm*a

aTechnische Universität Braunschweig, Institute of Inorganic and Analytical

Chemistry, Hagenring 30, 38106 Braunschweig


Over the past years the coordination chemistry with transition metals and main-group chemistry of the imidazolin-2-iminato ligands has been widely studied.1

The NHC moiety is capable to stabilize a positive charge, leading to highly basic ligands that can act as 2σ,4π-electron donors.

N

NR

R

N_

_ N

NR

R

N

__ _2

Herein, we introduce the imidazolin-2-iminato ligand to late transition metals (Fe, Co, Ru). We report about the synthesis of these low-coordinate metal complexes, their magnetic and electronic properties as well as their reactivity.

1 X. Wu, M. Tamm, Coord. Chem. Rev. 2014, 260, 116-138. T. Ochiai, D. Franz,

S. Inoue, Chem. Soc. Rev. 2016, 45, 6327-6344

Poster 23

52

Poster 24

Catalytic, Enantioconvergent Coupling of Racemic Allenylic Carbonates and Alkylzinc Reagents

David Petrone,a Mayuko Isomura,a Ivan Franzoni,b Erick Carreira*a

a ETH Zürich, Vladimir-Prelog-Weg 3, HCI H335, 8093 Zürich, Switzerland.

b Department of Chemistry, University of Toronto, Toronto, Canada, M5S 3H6.

*e-mail: [email protected]

The first enantioconvergent C(sp3)−C(sp3) coupling between racemic allenylic electrophiles and alkylzinc reagents has been developed. A Ir/(phosphoramidite,olefin) catalyst has been employed to overcome the shortcomings of conventional Pd/phosphine-based catalysts by affording access to highly enantioenriched allenylic substitution products with complete regiocontrol over the corresponding diene isomers. 1

Furthermore, since this reaction exploits, yet conserves the key allene moiety, the products obtained can be used in a variety of highly stereoselective transformations as means to increase molecular complexity.

1 Petrone, D.A.; Isomura, I.; Franzoni, I.; Carreira, E.M. In Preparation.

53

Intermolecular Radical Addition to Carbonyls Enabled by Visible Light Photoredox Initiated Hole Catalysis

Lena Pitzera, Frank Gloriusa*

aInstitute of Organic Chemistry, Westfälische Wilhelms-Universität Münster,

Corrensstr. 40, 48149 Münster, Germany


Over the last decade visible light photoredox catalysis has emerged as a powerful tool that allows for selective generation of radicals under mild conditions. In most cases, if not functionalized, these radicals were trapped with weak C–Xdouble bonds (X = C or N). However, applying simple carbonyl compounds such as aldehydes or ketones as intermolecular radical acceptors has yet only been described once.[1] This is due to the formation of a thermodynamically unfavourable alkoxy radical, which preferably decays via C–C β-scission. We found that the regioselective addition of alkyl radicals toaldehydes or ketones can be achieved by Brønsted acids-mediated hole catalysis. Under photoredox initiation the corresponding alcohols can be obtained in good yields.[3]

[1] a) Clerici, A.; Porta, O.; Zago, P. Tetrahedron 1986, 42, 561. b) Clerici, A.;

Porta, O. J. Org. Chem. 1989, 54, 3872.

[3] Pitzer, L.; Sandfort, F.; Strieth-Kalthoff, F.; Glorius, F. J. Am. Chem.

Soc. 2017, 139, 13652-13655.

Poster 25

54

Ortho-Substituted Arylsilanes in Oxidative Gold CatalysisMatthew Robinsona and Guy Lloyd-Jones*a

aUniversity of Edinburgh, UK


Oxidative gold catalysis is emerging as a powerful synthetic tool due to the unique reactivity of gold in comparison to the other late transition metals.1 Our group recently reported the first gold-catalysed oxidative coupling of arylsilanes and arenes to form functionalised biaryls.2

Previous Work:

SiMe3

+H

[Au] cat. (2 mol%)IBDA (1.3 equiv)

RSO3H (1.5 equiv)

CHCl3, rt

R

RThis Work:

SiMe3R

• Synthesis• Reactivity• Applications

One limitation of the chemistry, however, is the profound unreactivity of arylsilanes bearing ortho-substitution. Seeking to address this gap in reactivity, we have investigated the transmetalation of these reagents under catalytically relevant conditions, using a combination of in situ reaction monitoring and kinetic modelling.

1 Hopkinson, M. N.; Gee, A. D.; Gouverneur, V. Chem. Eur. J. 2011, 17,

8248−8262.

2 Ball, L. T.; Lloyd-Jones, G. C.; Russell, C. A. Science 2012, 337, 1644−1648.

Poster 26

55

Base Metal-Catalyzed C–H Functionalizations Nicolas Sauermann,a Lutz Ackermann*a

aInstitut für Organische und Biomolekulare Chemie, Georg-August-Universität

Göttingen, Tammannstraße 2, 37077 Göttingen (Germany)

e-mail: [email protected]goettingen.de

Base metal-catalyzed C–H activation represents a powerful synthetic alternative to costly and rare 4d and 5d transition metals in C-H activation chemistry. 1 In recent years, tremendous progress has been achieved, especially with cost effective and less toxic iron,2 manganese,3 cobalt4 and nickel5 catalysis regimes for C–H activation. 1 a) Song, G.;; Li, X. Acc. Chem. Res. 2015, 48, 1007–1039. b) Segawa, Y.;;

Maekawa, T.;; Itami, K. Angew. Chem. Int. Ed. 2015, 54, 66–81. 2 Cera, G.;; Ackermann, L. Top. Curr. Chem. 2016, 374, 57. 3 Liu, W.;; Ackermann, L. ACS Catal. 2016, 6, 3743–3752. 4 Moselage, M.;; Li, J.;; Ackermann, L. ACS Catal. 2016, 6, 498–525.

5 a) Ruan, Z.;; Lackner, S.;; Ackermann, L. Angew. Chem. Int. Ed. 2016, 55,

3153–3157. b) Castro, L. C. M.;; Chatani, N. Chem. Lett. 2015, 44, 410–421.

Poster 27

56

Enantioselective Formation of Acyclic Quaternary Carbon Stereocenters Through Allene Hydrohydroxymethylation

Leyah A. Schwartz and Michael J. Krische*

University of Texas at Austin, Department of Chemistry (A5300)

AUSTIN, TX 78712-0165


Catalytic enantioselective formation of acyclic quaternary carbon stereocenters remains a major challenge in chemical synthesis. The asymmetric generation of CF3-bearing quaternary carbon stereocenters represents an even greater challenge. Using the concepts of alcohol mediated C–C carbonyl addition pioneered in the Krische laboratory, we have developed an iridium catalyzed C–C coupling of methanol with CF3-bearing allenes. Notably, this process delivers acyclic CF3-substituted quaternary carbon stereocenters with high levels of enantioselectivity in the absence of stoichiometric metals or byproducts.

1 Holmes, M.;; Nguyen, K. D.;; Schwartz, L. A.;; Luong, T.;; Krische, M. J. J. Am.

Chem. Soc. 2017, 139, 8114-8117.

Poster 28

57

Asymmetric Hydrogen Bond Donor Catalyzed Oxetane Opening Enabled by Transition State Stabilization

Strassfeld,a Wickens,a Algera,a Jacobsen*a

aDepartment of Chemistry and Chemical Biology, Harvard University,

Cambridge, Massachusetts 02138 USA


Dual hydrogen bond donor catalysts were shown to activate silicon halides to catalyze the asymmetric intermolecular ring opening of a broad range of prochiral oxetane substrates, producing densely functionalized chiral building blocks bearing orthogonal functionality for further derivatization (alcohol and

halide).1 Mechanistic studies indicate that the catalyst controls selectivity-determining collapse of an oxonium halide ion-pair using non-covalent stabilizing interactions. Transition state stabilization by the chiral catalyst allows for selective reaction even in the presence of other hydrogen bond donors. Thus co-catalysis by chiral and achiral hydrogen bond donor catalysts allows for significant rate acceleration from the achiral catalyst without loss in enantioselectivity. 1 Wickens, Z. K.;; Strassfeld, D. A.;; Jacobsen, E. N. manuscript in preparation.

Poster 29

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Poster 30

Diastereoselective Cobalt-Catalyzed Cross-Couplings of Bench-Stable Alkynylzinc Pivalates with Cycloalkyl

Halides Lucie Thomasa and Paul Knochela

a Department of Chemistry, Ludwig-Maximilians-Universität München,

Butenandtstr. 5-13, Haus F, 81377 Munich, Germany


Alkynes play an important role in the synthesis of natural products and bioactive molecules.1 Transition-metal catalyzed cross-coupling reactions are indispensable tools for the introduction of the alkynyl unit into organic molecules. Especially Negishi cross-couplings show several crucial benefits, such as high functional group tolerance and also low toxicity. 2 Recent advances have shown that air stable alkynylzinc pivalates can undergo cobalt-catalyzed cross-coupling. 3 Herein we report a diastereoselective cobalt-catalyzed cross-coupling of bench-stable alkynylzinc pivalates with various cycloalkyl halides. 4 1 (a) Liu, J.; Lam, J. W. Y.; Tang, B. Z. Chem. Rev. 2009, 109, 5799-5867. b)

Bisoyi, H. K.; Kumar, S. Chem. Soc. Rev. 2010, 39, 264-285. 2 Negishi, E.; Anastasia, L. Chem. Rev. 2003,103, 1979-2008. 3 Thomas, L.; Hammann, J. M.; Chen, Y.-H.; Haas, D.; Knochel, P. Org. Lett.

2017, 19, 3847-3850. 4 Thomas, L.; Knochel, P. 2018, manuscript in preparation.

59

Ni-Catalyzed Dicarboxylation of 1,3-Dienes with CO2 Andreu Tortajada,a Ryo Ninokata, a Ruben Martin*a,b

a Institute of Chemical Research of Catalonia (ICIQ), The Barcelona Institute of Science and Technology, Av. Països Catalans 16, 43007 Tarragona (Spain)

b ICREA, Passeig Lluís Companys 23, 08010 Barcelona (Spain)


In recent years, the development of metal-catalyzed reductive carboxylation of organic (pseudo)halides with carbon dioxide (CO2) for preparing carboxylic acids have become powerful alternatives to the classical use of well-defined, and in most instances, air-sensitive organometallic species. 1 From a both atom- and step-economical standpoint, it would be ideal to design catalytic carboxylation protocols using unsaturated hydrocarbons. Additionally, it holds great promise to provide a new technological push towards the conversion of raw materials into valuable products.2 In this communication a novel nickel-catalyzed dicarboxylation of 1,3-dienes with CO2 will be presented for the synthesis of carboxylic acids. 1 Börjesson, M.;; Moragas, T.;; Gallego, D.;; Martin, R. ACS Catalysis 2016, 6,

6739-6749 2 Juliá-Hernández, F.;; Gaydou, M.;; Serrano, E.;; Van Gemmeren, M.;; Martin, R. Top Curr Chem (Z) 2016, 374:45

Poster 31

60

Intermolecular Desymmetrizing Gold-Catalyzed Yne-Yne-Reaction of Push-Pull Diarylalkynes Vanessa Weingand,a A. Stephen K. Hashmi*a,b

a Organisch-Chemisches Institut, Ruprecht-Karls-Universität Heidelberg Im Neuenheimer Feld 270, 69120 Heidelberg (Germany)

b Chemistry Department, Faculty of Science King Abdulaziz University, Jeddah 21589, Saudi Arabia

e-mail: [email protected]heidelberg.de

Push-pull diarylalkynes are dimerized in the presence of a cationic gold catalyst. The polarized structure of the substrates enables the generation of a highly reactive vinyl cation[1] in an intermolecular reaction. Trapping of the cation by a nucleophilic attack of an aryl unit leads to the formation of naphthalenes.

[1] T. Wurm, J. Bucher, S. B. Duckworth, M. Rudolph, F. Rominger, A.

S. K. Hashmi, Angew. Chem. 2017, 129, 3413-3417, T. Wurm, J.

Bucher, S. B. Duckworth, M. Rudolph, F. Rominger, A. S. K. Hashmi,

Angew. Chem. Int. Ed. 2017, 56, 3364-3368.

Poster 32

61

Inducing Axial-Chirality in a Supramolecular Catalyst Katharina Wenz,a Bernhard Breit, *a

a Institut für Organische Chemie

Albert-Ludwigs-Universität Freiburg


A new type of self-assembly ligand able to form axial-chiral, supramolecular complexes was designed through DFT calculations: two chiral monomers, each featuring a covalently bound chiral auxiliary, form a bidentate phosphine ligand with a twisted, hydrogen-bonded backbone upon coordination to atransition metal center, resulting in two diastereomeric, troposcomplexes. The ratio of the diastereomers in solution is very temperature- and solvent-dependent: rhodium- and platinum complexes were analyzed through a combination of NMR-studies, ESI-MS measurements, as well as UV-VIS and circular dichroism spectroscopy. The chiral self-organizedligands were evaluated in the rhodium-catalyzed asymmetric hydrogenation of α-dehydrogenated amino acids resulting in good conversion and high enantioselectivity. This opens the way for new ligand designs based on stereocontrol of supramolecular assemblies through stereodirecting chiral centers.

Poster 33

62

Poster 34

Direct Asymmetric Ruthenium-Catalyzed Reductive Amination of Alkyl−Aryl Ketones with NH3/H2

Marko Hermsen,a,b,* Jedrzej Wysocki,a Joan Gallardo-Donaire,a,* Martin Ernst,b Frank Rominger,d Oliver

Trapp,a,e A. Stephen K. Hashmi,a,d Ansgar Schafer,b Peter Comba,a,f Thomas Schaub*,a,b

aCatalysis Research Laboratory (CaRLa), Im Neuenheimer Feld 584, 69120 Heidelberg, Germany ; bBASF SE, Carl-Bosch-Strasse 38, 67056

Ludwigshafen, Germany ; dOrganisch-Chemisches Institut, Heidelberg University, Im Neuenheimer Feld 270, 69120 Heidelberg, Germany ;

eDepartment Chemie, Ludwig-Maximilians-Universitat Munchen, Butenandtstr. 5-13, 81377 München, Germany ; fAnorganisch-Chemisches Institut,

Heidelberg University and Interdisciplinary Center for Scientific Computing (IWR), Im Neuenheimer Feld 270, 69120 Heidelberg, Germany


The asymmetric ruthenium-catalyzed reductive amination employing ammonia and hydrogen to primary amines is described. Here we demonstrate the capability of our catalyst to perform a chemo- and enantioselective process while using simple ammonia gas as a reagent, one of the most attractive and industrially relevant nitrogen sources. The presence of a catalytic amount of ammonium iodide was essential for obtaining good yields and enantioselectivities. The mechanism of this reaction was investigated by DFT and we found a viable pathway that also explains the trend and magnitude of enantioselectivity through the halide series in good agreement with the experimental data.

The in-depth investigation of substrate conformers during the reaction turned out to be crucial in obtaining an accurate prediction of the enantioselectivity. Furthermore, we report the crystallographic data of the chiral [Ru(I)H(CO)((S,S)-f-binaphane)(PPh3)] complex, which we identified as the most efficient catalyst in our investigation. J. Gallardo-Donaire et al., J. Am. Chem. Soc. 2018, 140 (1), 355–361.

63

The in-depth investigation of substrate conformers during the reaction turned out to be crucial in obtaining an accurate prediction of the enantioselectivity. Furthermore, we report the crystallographic data of the chiral [Ru(I)H(CO)((S,S)-f-binaphane)(PPh3)] complex, which we identified as the most efficient catalyst in our investigation. J. Gallardo-Donaire et al., J. Am. Chem. Soc. 2018, 140 (1), 355–361.

64

Poster 35

Photoinduced Direct Conversion of Cyclohexaneinto Cyclohexanone Oxime using LEDs

Jędrzej Wysocki,a Joaquim Henrique Teles,b Richard Dehn,b

Oliver Trapp,a,c Bernd Schäfer,b Thomas Schaub *,a,b

aCaRLa, Im Neuenheimer Feld 584, 69120 Heidelberg (Germany)bBASF SE, Carl-Bosch-Str. 38, 67056 Ludwigshafen (Germany)cDepartment Chemie, Ludwig-Maximilians-Universität München,

Butenandtstr. 5–13, Haus F, 81377 München (Germany)


A selective direct photochemical transformation of cyclohexane into cyclohexanone oxime using tert-butyl nitrite and UV LED diodes is described. The reaction allows the direct introduction of an oxime group into a hydrocarbon using a simple set-up in one step that proceeds in a clean fashion, a transformation which technically would require several steps. Thisstraightforward method may provide a valuable alternative tosignificantly more expensive common procedures for the synthesis of cyclohexanone oxime, a key precursor to the Nylon-6 polymer.

HH NOH

ONO

J. Wysocki, J. H. Teles, R. Dehn, O Trapp, B. Schäfer, T. Schaub,

ChemPhotoChem 2017, doi: 10.1002/cptc.201700151.

11th carla winter school 2018...

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