9th carla winter school 2016 heidelberg

9th CaRLa Winter School 2016

Heidelberg

February 21-26, 2016

Final Program

Welcome to the 9th 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 21-26, 2016 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 23), were we will have the poster session during the lunch break (lunch is provided). 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 Oliver Trapp

3

INDEX

1. Welcome Message 3

2. Index 4

3. Program 5

4. Lecture Sessions 10

5. Poster Abstracts 24

6. List of Lecturers 60

7. List of Participants 61

8. Hotel Map 65

9. Map of Lunch Venues 66

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SUNDAY • 21st February

Until 16:00 Arrival and Welcome Coffee

16:30 Opening Ceremony Oliver Trapp

17:00 Keynote Lecture BASF Henrique Teles

18:00 Light Dinner and Get-Together

MONDAY • 22nd February

09:00 Session Scott Miller

10:00 Coffee Break

10:15 Session Scott Miller

11:15 Coffee Break

11:30 Flash Poster Presentation

12:00 Free Time (Lunch)

14:30 Session Magnus Rueping

15:30 Coffee Break

15:45 Session Magnus Rueping

16:45 Coffee Break


18:00 Light Dinner

6

TUESDAY • 23rd February

09:00 Session Peter Comba

10:00 Coffee Break

10:15 Session Peter Comba

11:15 Coffee Break

11:30 Lunch and Poster Session

14:30 Session Guy Lloyd-Jones

15:30 Coffee Break

15:45 Session Guy Lloyd-Jones

16:45 Coffee Break


18:00 Free Time

7

WEDNESDAY • 24th February

09:00 Session Tobias Ritter

10:00 Coffee Break

10:15 Session Tobias Ritter

11:15 Coffee Break


12:00 Free Time (Lunch)

14:30 Session Aiwen Lei

15:30 Coffee Break

15:45 Session Aiwen Lei

16:45 Coffee Break


18:00 Light Dinner

8

THURSDAY • 25th February

09:00 Session Todd Marder

10:00 Coffee Break

10:15 Session Todd Marder

11:15 Lunch and Poster Session

13:00 Excursion to BASF

18:00 Symposium Dinner

FRIDAY • 26th February

09:00 Session Mark Saeys

10:00 Coffee Break

10:15 Session Mark Saeys

11:15 Coffee Break

11:30 Poster Price Ceremony and Closing Remarks

12:00 Departure

9

Lecture Sessions

10

Catalytic oxidation reactions with high-valent transition

metal complexes: background and applications

Peter CombaAnorganisch-Chemisches Institut and Interdisziplinäres Zentrum für

Wissenschaftliches Rechnen, Universität Heidelberg

e-mail: [email protected]

While the enzymatic oxidation of methylene groups is a fundamental transformation in biological systems, the selective oxidation of saturated C-H bonds still is a challenge in synthetic organic chemistry. The still short history of nonheme iron model systems will be briefly reviewed, followed by an overview of published and possible future applications in the area of organic synthese and energy conversion.

11

Catalytic oxidation reactions with high-valent transition

metal complexes: ligand control of structure, electronics

and reactivity

Peter CombaAnorganisch-Chemisches Institut and Interdisziplinäres Zentrum für

Wissenschaftliches Rechnen, Universität Heidelberg


Substrate scope and product selectivity are known to depend on the shape of a reactive center, in transition metal complexes obviously on the coordination chemistry and therefore on the ligand structure. It also emerges that the spin- and oxidation state, the redox potential and the reactivity of, e.g., ferryl complexes emerge from their structure. Examples of tunable structures, redox properties and reactivities of nonheme oxo-metal complexes and the influence of structures on reaction pathways will be discussed on the basis of a combination of experimental and computational data.

12

Radical C-H Activation / Oxidative Coupling, Reactions and MechanismLei Aiwen

College of Chemistry and Molecular Sciences, Wuhan University, Wuhan 430072, China

[email protected]

Our research focuses on the oxidative coupling to develop a novel and efficient bond-formation method between two nucleophiles. We

have successfully developed four generations of oxidative coupling. In addition, in-depth understanding toward the reactions is the other focus. New insights into the reaction mechanism have been revealed by operando X-ray absorption, Raman, EPR, and NMR spectroscopy.1

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(a) Liu, C.; Zhang, H.; Shi, W.; Lei, A. W., Chem. Rev. 2011, 111, 1780-1824; (b) C. Liu, D. Liu, A. Lei, Acc.

Chem. Res. 2014, 47, 3459; (c) He, C.; Zhang, G. H.; Ke, J.; Zhang, H.; Miller, J. T.; Kropf, A. J.; Lei, A. W., J.

Am. Chem. Soc. 2013, 135, 488-493. (d) Zhang, G. T.; Liu, C.; Yi, H.; Meng, Q. Q.; Bian, C. L.; Chen, H.; Jian,

J. X.; Wu, L. Z.; Lei, A. W., J. Am. Chem. Soc. 2015, 137, 9273-9280.

13

2B or not 2B and other mix-ups

Guy Lloyd-Jones *a

aSchool of Chemistry, University of Edinburgh, Edinburgh, EH9 2FJ, Scotland


The presentation will focus on the in situ analysis and development of reactions of interest to the synthetic chemist, particularly those employing reagents based on boron or silicon. The work aims to gain a better grasp of the fundamental physical and chemical processes that facilitate and govern the reaction of interest, either directly or via modulation of undesired side reactions. The approach is predominantly mechanistic elucidation via analysis of reaction kinetics and

other physical organic parameters, obtained by UV, IR, MS, and NMR in concert with strategic isotopic labelling, and augmented by computational analysis. The presentation will also introduce details of new devices for the efficient exploration of reaction kinetics in situ that can be quickly and simply coupled to standard laboratory instruments.1

1 Lloyd-Jones, G.C.; Gonzalez, J.; Cresswell, A. J.; Corrie T.J.A.; Reid. M.;

Dooley, R.; Jones, A.; unpublished. 2015.

14

Snakes and Ladders in the Investigation of Mechanism

Guy Lloyd-Jones *a

aSchool of Chemistry, University of Edinburgh, Edinburgh, EH9 2FJ, Scotland


The presentation / problem class will take stock of what we mean by ‘reaction mechanism’, why it is useful, and how we explore it. Over the last 50 years or so, there has been a tremendous evolution of the instrumentation and technology available, with various tools coming into use, and others going out of fashion. Indeed, much can now be quickly elucidated using standard laboratory facilities and instrumentation. Nonetheless, it still remains easy to be to be fooled by

mechanism, even of what are very simple processes in the context of the dazzling array of methodologies now available for catalysis and synthesis. Drawing predominantly on case studies from the authors laboratories, we will explore examples of successful techniques and investigations (the "ladders"), as well as the pitfalls en route (the "snakes"), perhaps with some indications on how to avoid falling into similar ones yourself.

15

Transition Metal Catalyzed Borylation of C-H and C-XBonds: Synthesis of Aryl and Alkyl Boronates

Todd B. MarderInstitut für Anorganische Chemie, Universität Würzburg, Germany


Arylboronate esters are of great importance in synthesis, as substrates for Suzuki-Miyaura coupling, conjugate additions, and conversion to many functional groups. New routes to arylboronates include Pd or Ni-catalyzed cross-coupling reactions of alkoxydiboron or alkoxyborane reagents with aryl halides, and more recently, the selective iridium catalyzed C-H-borylation of aromatic substrates. The lecture will present

some of our work on the Ir-catalyzed borylation of aromatic C-Hbonds, applications (e.g., to pyrene chemistry) and issues affecting selectivity, and our recent development of inexpensive Cu and Zn-catalysts for the borylation of aryl- as well as alkyl halides.1-3

1 Bose, S.K.; Deißenberger, A.; Eichhorn, A.; Steel, P.G.; Lin, Z.; Marder, T.B.

Angew. Chem. Int. Ed. 2015, 54, 11843.

2 Ji, L.; Lorbach, A.; Edkins, R.M.; Marder, T.B. J. Org. Chem. 2015, 80, 5658.

3 Ji, L.; Fucke, K.; Bose, S.K.; Marder, T.B. J. Org. Chem. 2015, 80, 661.

16

Fundamental Steps Involved in Cross-Coupling Reactions

Todd B. MarderInstitut für Anorganische Chemie, Universität Würzburg, Germany


Cross-coupling reactions, usually catalyzed by Pd or Ni, typically involve a sequence of elementary steps including oxidative addition, transmetallation, and reductive elimination.The discussion we will have will focus on aspects of these elementary steps which, after several decades of research and numerous applications, still remain subjects of controversy. For example, there still remain questions of how many ligands are on a Pd(0) complex when oxidative addition of an arylhalide

occurs, with various proposals of 1, 2 or even 3 ligands being present. Could all these be possible? Could this depend on the substrate, the ligand or other factors? What general factors govern the efficiency of transmetallation processes? What is the difference between boron and silicon or tin reagents with regard to the transmetallation step? What about aryl vs. alkyl groups? Why are some reductive elimination reactions faster than others? Thus, our discussion will examine these general

issues and both experimental and theoretical results which shed light on them.

17

Searching for Selective Reactions on Complex Molecular Scaffolds

Scott J. MillerDepartment of Chemistry, 225 Prospect Street, Yale University, New Haven, Connecticut 06520-8107,

USA

Email: [email protected]

Natural products have provided perennial inspiration for the development of synthetic

methods, and enzymes have provided an analogous platform for the conception of new catalysts. This lecture will recount an interplay of experiments stimulated by

these two major classes of naturally occurring substances. Specifically, the

discovery and use of peptides as catalysts for a variety of asymmetric bond formations will be presented. Likewise, applications of these catalysts to the

synthesis and selective modification of complex molecules, including biologically

active natural products, will be described. A particular emphasis will be placed on reactions that present unusual stereochemical challenges. An analysis of catalyst

types that may be brought to bear on complex molecular environments will also be

included.

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18

Searching for Selective Reactions on Complex Molecular Scaffolds


USA


Natural products have provided perennial inspiration for the development of synthetic

methods, and enzymes have provided an analogous platform for the conception of new catalysts. This lecture will recount an interplay of experiments stimulated by

these two major classes of naturally occurring substances. Specifically, the

discovery and use of peptides as catalysts for a variety of asymmetric bond formations will be presented. Likewise, applications of these catalysts to the

synthesis and selective modification of complex molecules, including biologically

active natural products, will be described. A particular emphasis will be placed on reactions that present unusual stereochemical challenges. An analysis of catalyst

types that may be brought to bear on complex molecular environments will also be

included.

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Catalysis: Asymmetric, Enzymatic, Biomimetic, Inorganic, Organometallic, Organocatalytic – Are These Separate Fields and

What is Next?


USA


In 1836, Berzelius discussed “Considerations Respecting a New Power Which Acts in

the Formation of Organic Bodies” in his famous paper published in the Edinburgh

Philosophical Journal (Edinburgh New Philos. J. 1836, 21, 223.) Catalysis as an intellectual construct for the accelerated interconversion of matter has been intensely

studied in the aftermath. Enzymes and nonenzymatic catalysts dominate large

swaths of the scientific literature to this day. The late Professor Jeremy Knowles wondered out loud about the paradox, “Enzymatic Catalysis: Not Different, Just

Better” in a famous essay (Nature 1991, 350, 121-124). What did he mean? What have been the major advances in the field of catalysis since? If Berzelius andKnowles were attending the CaRLa Winter School this year, what would their

assessment of the field be? This lecture will recount some of the major advances in

the field of catalysis, analyzing some historically important papers. Do these landmark works show the way to what is next? Or are there other important factors

driving the field forward?

19

Late-Stage Fluorination for PET Imaging Ritter Tobias

Department of Organic Synthesis, Max-Planck-Institut für Kohlenforschung,

Kaiser-Wilhelm-Platz 1, 45470 Mülheim an der Ruhr, Germany.

Department of Chemistry and Chemical Biology, Harvard University

12 Oxford Street Cambridge, MA 02138 USA.

Department of Radiology, Massachusetts General Hospital

55 Fruit Street Boston, MA 02114 USA.

[email protected]

The unnatural isotope fluorine–18 (18F) is used as a positron emitter

in molecular imaging. Currently, many potentially useful 18F-labeled

probe molecules are inaccessible for imaging because no fluorination

chemistry is available to make them. Syntheses must be rapid on

account of the 110-minute half-life of 18F and benefit from using

[18F]fluoride due to practical access and suitable isotope enrichment.

But [18F] fluoride chemistry has been limited to nucleophilic

fluorination reactions. I will describe the development of a

palladium-based electrophilic fluorination reagent derived from

fluoride and its application to the synthesis of aromatic 18F-labeled

molecules via late-stage fluorination. In addition, I will discuss new

reaction chemistry for introduction of fluorine into functionalized

molecules. Late-stage fluorination enables the synthesis of

conventionally unavailable positron emission tomography (PET)

tracers for anticipated applications in pharmaceutical development as

well as pre-clinical and clinical PET imaging.

20

Modeling-Guided Design of Homogenous Catalysts

Mark SaeysLaboratory for Chemical Technology, Ghent University

Technologiepark 914, 9052 Ghent, Belgium


Catalyst design and kinetic modeling often start from molecular-scale hypotheses about the reaction mechanism, the structure of the active catalyst and the nature of the rate and selectivity determining steps. Computational catalysis has become a crucial tool to analyze molecular-scale concepts and elucidate their electronic origin. In combination with characterization and experimental kinetic validation, insights gained from computational catalysis can be translated all the way to the industrial scale. This pas-de-deux between experiment and theory is becoming the new paradigm incatalyst design and kinetic modeling, both in academia and in industry.

I will illustrate how this approach led to the discovery of the first nucleophilic aryl-fluorination catalyst using a mono-dentate Pd catalyst, which was experimentally validated in the Buchwald group, and, in collaboration with the experimental group of Professor Hierso, identified a novel reductive elimination pathway for challenging C-O and C-S coupling reactions through an unusual penta-coordinated transition state. The

21

“hemi-lability” of these HiersoPhos ligands is governed by a tug-of-war between enthalpy and entropy, and is expected to be beneficial for many challenging Pd-catalyzed reactions. For all examples, it will be illustrated how molecular-scale modeling provides insight into the electronic and bonding effects that govern catalyst structure and activity.

During the second presentation, the use of computational chemistry to guide catalyst discovery and to elucidate the structure of reaction intermediates and products will be illustrated with several examples.

ReferencesNandula, Trinh, Saeys, Alexandrova, Angew. Chem. Int. Ed.,

2015Platon, Wijaya, Rampazzi, Cui, Rousselin, Saeys, Hierso,

Chem Eur J, 2014 Saeys, Buchwald, Watson, Su, Teverovskiy, PCT/US2010

/041308, 2011Platon, Cui, Mom, Richard, Saeys, Hierso, Adv. Syn. Cat.,

2011 Cui, Saeys, ChemCatChem, 2011

22

Zeolite catalyzed oxidations with H2O2

Teles, J. Henriquea

aBASF SE, Ludwigshafen, Germany


In an industrial context, oxidations with hydrogen peroxide using metal substituted zeolites are increasingly gaining importance. 1 Developments started about a quarter of a century ago with the discovery of titanium silicalite (TS-1) and since then several processes were developed or are under development using titanium zeolites. In recent years, tin containing zeolites have attracted increased attention. This

lecture will give a current view on the use of zeolites as catalysts for oxidations with hydrogen peroxide in the chemical industry.

1 a) J. H. Teles, I. Hermans, G. Franz, R. A. Sheldon, in Ullmann’s

Encyclopedia of Industrial Chemistry, Published online: 23 Jul 2015, DOI:

10.1002/14356007.a18_261.pub2; b) F. Cavani, J. H. Teles, ChemSusChem,

2009, 2, 508-534

23

24

Poster Abstracts

CaRLa – The Catalysis Research Laboratory Oliver Trapp*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.Unlike in a classic collaboration between industry and academia, there is a tight scientific guidance of the postdoctoral researchers due to a dedicated BASF lab head in place. In this setting, currently at least 8 postdocs are working together on various projects in the area of transition metal based homogeneous catalysis. The team is also supported by a lab technician and co-workers from the quantum chemical group of the BASF.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.

25

Poster 1

Synthesis and Properties of Helicene RuthenocenesAkiyama Midori,a Tsuchiya Yuto,b Ishii Ayumi,b

Hasegawa Miki,b Kurashige Yuki,c Nozaki Kyoko*a

aDepartment of Chemistry and Biotechnology, Graduate School of Engineering,

The University of Tokyo, Japan; bDepartment of Chemistry and Biological

Science, College of Science and Engineering, Aoyama Gakuin University,

Japan; cInstitute for Molecular Science, Japan.


Three types of ruthenocenes coordinated by dinaphtho[2,1-c:1',2'-g]fluorenyl (Dnf) anion(s), a [7]helicene having a cyclopentadienyl moiety at the center of its skeleton, were synthesized: Those are, mono-helicene ruthenocene 1 having one Dnf bound to one Ru atom, bis-helicene ruthenocene 2 with two Dnfs, and bimetallic ruthenocene 3 in which two Ru atoms

are bound to a Dnf in 5 and 6 manners. Since Dnf has high racemization barrier, each of their enantiomers could be isolated in its pure form, which showed large optical rotation and intense response in circular dichroism (CD). Although 1 and 2 did not show any emission even at 77 K, bimetallic complex 3 exhibited phosphorescence in both solution (31%, 77 K in BuCN) and solid state (18%, 77 K).

26

Poster 2

Catalytic, Stereoselective Difluorination of AlkenesSteven M. Banik,a Jonathan W. Medley,a Eric N. Jacobsen*a

aDepartment of Chemistry and Chemical Biology, Harvard University, Cambridge, MA,

02138, USA.


The dihalogenation of alkenes is a foundational transformation that is not only of widespread synthetic utility, but has provided a classical framework for understanding the stereochemical outcomes of reactions. Despite the dramatic impact fluorine-containing molecules have had on the landscape of molecular design, the development of direct and general alkene difluorination methods has lagged behind that of analogous dibromination and dichlorination reactions, particularly with respect to relative stereocontrol. We describe a

catalytic, diastereoselective 1,2-difluorination of a broad range of alkenes utilizing a commercially available nucleophilic fluoride source and oxidant in conjunction with hypervalent iodine catalysis.1 The resulting stereochemical relationship between vicinal fluorides in several products suggests anchimeric assistance as a plausible mechanistic pathway with implications for fluorinated building block construction.

[1] S.M. Banik, J.W. Medley, E.N. Jacobsen. Submitted.

27

Poster 3

Palladium-Catalyzed Transannular C–H Functionalization

of Alicyclic Amines

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

aDepartment of Chemistry, University of Michigan, 930 N. University Ave, Ann

Arbor, Michigan 48109, United States


The conversion of carbon-hydrogen (C–H) bonds into new functional groups (FG) represents a powerful strategy for the synthesis of organic molecules. Despite tremendous progress in the field, selective C–H functionalization can still only be achieved in the context of a limited set of organic substrates

and C–H sites. One class of substrates that has proven particularly challenging for selective C–H functionalization is aliphatic amines. This report describes a new approach that enables the selective C–H arylation of diverse alicyclic amine cores by harnessing the strongly donating properties of the sp3-nitrogen atom to direct metal catalysts at specific C–Hbonds that are remote from nitrogen. This approach leverages the energetically disfavored boat conformation of these cyclic

substrates to achieve transannular C–H activation and subsequent C-FG bond formation. The design, optimization, and scope of this new transformation are described.

28

Poster 4

Using enzymes and bio-inspired catalysts to clean up organophosphate pesticides

Daumann, Lenaa; Gahan, Lawrenceb; Comba, Petera

aInstitute of Inorganic Chemistry, University of Heidelberg

bSchool of Chemistry and Molecular Biosciences, University of Queensland


Annually thousands of people die or suffer from organophosphate (pesticide) poisoning. In order to remove these compounds from the environment, the use of enzymes as bioremediators has been proposed.1 Here we will present dinuclear metalloenzymes and bioinspired complexes capable of cleaving organophosphates (OP). The promiscuous glycerophosphodiesterase (GpdQ) from Enterobacter

aerogenes was optimized with site directed mutagenesis while the activity of the biomimetic complexes towards OPs was increased by modifications in the ligand backbone. To generate a recyclable system GpdQ was further immobilized onto PAMAM dendrimer-modified magnetite nanoparticles. A kinetic assay was designed to evaluate the activity towards OPs and showed that the immobilized enzyme was active after multiple cycles and after a prolonged time period.

1 Hadler, K. S.; Mitić, N.; Ely, F.; Hanson, G. R.; Gahan, L. R.; Larrabee, J. A.;

Ollis, D. L.; Schenk, G. J. Am. Chem. Soc. 2009, 131, 11900-11908.

29

Poster 5

A Sustainable Multicomponent Pyrimidine SynthesisNicklas Deibl, Kevin Ament, Rhett Kempe*

University of Bayreuth, Chair of Inorganic Chemistry II, 95440 Bayreuth,

Germany


Dwindling fossil carbon resources and environmental concerns associated with their use call for alternative ways to produce fine chemicals. Alcohols are broadly accessible from indigestible biomass (lignocellulose)[1] which makes the conversion of alcohols to important classes of fine chemicals a central topic of sustainable synthesis. Multicomponent reactions are especially attractive in organic chemistry as they allow the synthesis of large libraries of diversely functionalized

products in a short time when run in a combinatorial fashion. Herein, we present a novel, regioselective, iridium catalyzed multicomponent synthesis of pyrimidines from amidines and up to three (different) alcohols. Only hydrogen and water are liberated in the course of the reactions. PN5P-Ir-pincer complexes, recently developed in our laboratory,[2] catalyze this sustainable multicomponent process most efficiently.[3]

[1] Vispute, T. P.; Zhang, H.; Sanna, A.; Xiao, R.; Huber, G. W. Science 2010,

330, 1222-1227. [2] Michlik, S.; Kempe, R. Nat. Chem. 2013, 5, 140-144.

[3] Deibl, N.; Ament, K.; Kempe, R. J. Am. Chem. Soc. 2015, 137, 12804-12807.

30

Poster 6

Direct Synthesis of Primary Amines via Ruthenium-Catalysed Amination of Ketones with Ammonia and Hydrogen

Joan Gallardo-Donaire,a Martin Ernst,b Oliver Trapp,a,b and Thomas Schaub,c,*,b

aCatalysis Research Laboratory (CaRLa), Im Neuenheimer Feld 584, 69120Heidelberg, Germany. bOrganisch-Chemisches-Institut, Ruprecht-Karls-Universität Heidelberg, Im Neuenheimer Feld 270, 69120 Heidelberg. cBASF SE, Synthesis and Homogeneous Catalysis, 67056 Ludwigshafen, Germany

E-mail: [email protected]

A highly selective reductive amination of ketones to primary amines with ammonia and hydrogen using a simple ruthenium catalyst has been developed. The protocol described constitutes an efficient and direct atom-economical approach en route to -methylbenzylamine derivatives. The presence of catalytic amounts of aluminum triflate turned out to be crucial for achieving high conversion towards primary amines, with the highest selectivity reported up to date with an NH3/H2

system. Our precatalyst and ligand are both commercially available and inexpensive. Moreover, twelve examples with yields up to 99% have been described.

31

Poster 7

Continuous Flow Metalations of Acyclic, Acrylate Derived

Substrates. Applications in the Synthesis of Butenolides

and Pyridazines

Ganiek Maximilian A.a Becker Matthias R.a Ketels Marthe, a

Knochel Paul*a

a Ludwig-Maximilians-Universität München, Department Chemie, Butenandtstr.

5-13, Haus F, 81377

München, Germany


Directed metalations have proven to be a practical, general approach for the functionalization of suited C-H bonds. 1 Wehave further extended the applicability of metalation reactions

with hindered amide base systems by using continuous flow setups which allow the fast conduction of these reactions under more convenient conditions with improved results. Hence the metalation of acrylate derived molecules was improved and highly functionalized products were obtained,2 which have broad use.

1 (a) Schlosser, M.; Angew. Chem. Int. Ed. 2005, 44, 380. (b) Haag, B.; Mosrin,

M.; Ila, H.; Malakhov, V.; Knochel, P. Angew. Chem. Int. Ed. 2011, 50, 9794.

2 (a) Becker, M. R.; Ganiek, M. A.; Knochel, P. Chem. Sci., 2015, 6 , 6649. (b)

Ganiek, M. A.; Becker, M. R.; Ketels, M.; Knochel, P. manuscript submitted

32

Poster 8

Phosgene-Free Synthesis of Isocyanates from Carbon Dioxide and Organyltin

Nicolas Germain,a Oliver Trapp,a,b Thomas Schaub*,a,c aCatalysis Research Laboratory (CaRLa) Im Neuenheimer Feld, Heidelberg/DE

bOrganisch-Chemisches Institut, Ruprecht-Karls-Universität Heidelberg/D

cBASF SE, Carl-Bosch-Str. 38, 67056 Ludwigshafen, Germany E

e-mail: nicolas.germain@carla-hd

Polyurethanes (PU) are polymers of ubiquitous importance in our society with application in foams, sealants and coatings. Methylene diisocyanate (MDI) and toluene diisocyanate (TDI) are amongst the most valuable PU. However, phosgene and HCl remain important issues of the isocyanates synthesis. Replacing phosgene by carbon dioxide offers a less expensive and user-friendly alternative. We developed a methodology for the reaction of dialkyltin(IV) dialkoxide with anilines in an

atmosphere of carbon dioxide . Urethanes were obtained after reaction of aniline derivatives with CO2 and 2 equivalents of dialkyltin(IV) dialkoxide. Moreover, urethanes were cleaved in situ into isocyanates. Importantly, tin alkoxide could also be regenerated. Further

investigations are ongoing to unravel the mechanism of the reaction and to improve it for potential industrial applications.

33

Poster 9

A Manganese Catalyst for Highly Reactive yet

Chemoselective Intramolecular C—H Amination

Jennifer Griffin,a M. Christina White*a

aUniversity of Illinois at Urbana-Champaign


Despite the significant synthetic potential of C—H oxidation, the development of small molecule catalysts that can selectively oxidize inert C(sp3)—H bonds while tolerating more reactive π-functionality remains an unsolved problem. A novel manganese catalyst, [Mn(tBuPc)], has been developed to intramolecularly aminate all types of C(sp3)—H bonds without oxidizing more reactive π-functionality, demonstrating an unprecedented balance between reactivity and selectivity for a

C—H oxidation reaction. 1 Catalyst [Mn(tBuPc)] effects the chemoselective, intramolecular amination of all types of C(sp3)—H bonds, including strong 1° aliphatic C—H bonds and propargylic C—H bonds, while maintaining stereospecificity and high functional group tolerance. Mechanistic studies suggest that the unique reactivity and selectivity of [Mn(tBuPc)] can be attributed to its mechanism of metallonitrene C—Hinsertion that lies between stepwise radical C—H

abstraction/rebound and concerted C—H insertion.

1 Paradine, S.M.*; Griffin, J.R.*; Zhao, J.; Petronico, A. L.; Miller, S.M.; White,

M.C. Nature Chem. 2015, 7, 987-994. *These authors contributed equally.

34

Poster 10

Bimetallic Cu/Pd Catalysts with Bridging Aminopyrimidinyl

Phosphines for Decarboxylative Cross-Couplings at

Moderate Temperatures

Dagmar Hackenberger,a Werner R. Thiel,a Lukas J. Gooßen*a

aFachbereich Chemie, TU Kaiserslautern, Kaiserslautern, Germany


A bimetallic catalyst system is presented that for the first time enables the decarboxylative cross-coupling of triflates with carboxylate salts at only 100 °C,1 which is more than 50 °C lower than with previous Cu/Pd-based systems. 2 The key feature of the catalyst system is a bidentate P,N-ligand

designed to bridge the Pd and Cu centers and thereby facilitating the rate-determining transmetalation step. The new protocol allows the coupling of a broad range of aryl triflates with various substituted 2-nitrobenzoates in good to excellent yields.

1 Hackenberger, D.; Song, B.; Grünberg, M.F.; Farsadpour, S.; Menges, F.;

Kelm, H.; Groß, C.; Wolff, T.; Niedner-Schatteburg, G.; Thiel, W.R.; Gooßen,

L.J. ChemCatChem 2015, 7, 3579-3588.

2 a) Gooßen, L.J.; Deng, G.; Levy, L.M. Science 2006, 313, 662-664. b) Song,

B.; Knauber, T.; Gooßen, L.J. Angew. Chem. Int. Ed. 2013, 52, 2954-2958.

35

Poster 11

Atom-Economical Dimerization Strategy by the Rhodium-Catalyzed Addition of Carboxylic Acids to

Allenes: Protecting-Group-Free Synthesis of Clavosolide AHaydl, A. M.; Breit, B.*

Institut für Organische Chemie, Albert-Ludwigs-Universität Freiburg

Albertstraße 21, 79104 Freiburg im Breisgau, Germany


Natural products of polyketide origin with a high level of symmetry, in particular C2-symmetric diolides, often possess many different noteworthy biological activities.1 An efficient way to this important structure motif was developed as part of a concise and highly convergent synthesis of clavosolide A.2

Featuring an atom-economic “head-to-tail” dimerization by

stereoselective rhodium-catalyzed addition of carboxylic acids to terminal allenes with coincidently constructing two new stereocenters, excellent yields and remarkable selectivities within the C2-symmetric core structures were obtained.

1 Kang, E. J.; Lee, E.; Chem. Rev. 2005, 105, 4348-4378.

2 Haydl, A. M.; Breit, B. Angew. Chem. Int. Ed. 2015, 54, 15530-15534.

36

Poster 12

Trifluoromethylthiolation of N-Heteroarenes and

Alkenes Roman Honeker, Johannes B. Ernst, R. Aleyda

Garza-Sanchez, Matthew N. Hopkinson, Frank Glorius*Westfälische Wilhelms-Universität Münster


Incorporation of fluorinated moieties is a routine strategy to tune the properties of bioactive compounds. Recently, much attention is being focused on the development of new methods for the introduction of the trifluoromethylthio group (CF3S).1 In2015, we reported the selective trifluoromethylthiolation of biologically relevant N-heteroarenes catalyzed by table salt.2

More recently, we developed the visible light-promoted trifluoromethylthiolation of simple alkenes employing dual photoredox/halide catalysis.3

1 X.-H. Xu, K. Matsuzaki, N. Shibata, Chem. Rev. 2015, 115, 731.

2 R. Honeker, J. B. Ernst, F. Glorius, Chem. Eur. J. 2015, 21, 8047.

3 R. Honeker, R. A. Garza-Sanchez, M. N. Hopkinson, F. Glorius, submitted.

37

Poster 13

Characterization of Solution-phase Organoiron Catalyst by

in situ XAFS Analysis

Takahiro Iwamoto,a,b,c Ryosuke Agata,a,b Hikaru Takaya,a,b and

Masaharu Nakamura*a,b

aIRCELS, ICR, Kyoto University, Uji, Kyoto 611-0011, bDepartment of Energy

and Hydrocarbon Chemistry, Graduate School of Engineering, Kyoto

University, Kyoto 615-8510, cCREST, JST.


Recently iron catalyzed cross-coupling reactions have regained much attention due to their unprecedented reactivity and the practical advantages, while the mechanistic investigations have not well progressed. Herein, we applied in situ XAFS analysis1 to characterize organoiron intermediates

in the aryl–alkyl coupling reaction of alkyl chlorides with aryl Grignard reagents in the presence of FeF3/SIPr.2 XAFSanalysis combined with DFTcalculation implied a ferrate complex, [FeF2(SIPr)(alkyl)]MgXwould form as a reactive intermediate.

1 Takaya, H.; Nakamura, M. et al. Bull. Chem. Soc. Jpn. 2015, 88, 410–418.

2 Nakamura, M. et al. Synthesis 2015, 47, 1733–1740.

38

Poster 14

Olefin metathesis - new catalysts, new applications

Kajetanowicz Anna, *a,b Czaban Justyna,a Milewski Mariusz,a

Sytniczuk Adrian,a Grela Karol*a,b

a Institute of Organic Chemistry, PAS, Kasprzaka 44/52, Warsaw, Poland b Biological and Chemical Research Centre, Faculty of Chemistry, University of

Warsaw, Żwirki i Wigury 101, Warsaw, Poland

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

Although olefin metathesis has emerged as a unique and powerful transformation for the inter-conversion of olefins in organic chemistry, improvements in the field are still required.Here recent developments on synthesis of the catalysts

preventing migration of double bond1 and those facilitating purification of the products 2 will be presented. Also the utilization of Ru-complexes in conversion of biomass into useful products will be mentioned.3

1 Kajetanowicz, A.; Milewski, M., Catal. Sci. Technol., submitted.

2 Kajetanowicz, A.; Czaban, J.; Krishnan, G. R.; Malińska, M.; Woźniak, K.;

Siddique, H.; Peeva, L. G.; Livingston, A. G.; Grela, K. ChemSusChem 2013, 6,

182.

3 Kajetanowicz, A.; Sytniczuka, A.; Grela, K. Green Chem., 2014, 16, 1579.

39

Poster 15

Stabilized Borata-Alkene Formation: Structural Features,

Reactions and Influence of the Countercation

Sonja Kohrt,a Steffen Dachwitz,a Constantin G. Daniliuc,a Birgit

Wibbeling,a Gerald Kehr,a Gerhard Erker*a

aOrganisch-Chemisches Institut, Westfälische Wilhelms-Universität Münster


Dimethylbenzofulvene added HB(C6F5)2 at the exocyclic indene double bond.1 A subsequent isomerization furnishedthe 1H and 3H borylindenes, whose treatment with LiTMP resulted in a clean deprotonation reaction to afford a borata-alkene. An ensuing crystal structure analysis indicated apronounced B=C double bond character regardless of the

countercation present. Intriguingly, the reaction with an additional equivalent of HB(C6F5)2 resulted in the clean hydroboration of the B=C double bond. Furthermore, theborata-alkene also underwent [4+2] cycloaddition reactions with chalcone derivatives and a formal [6+2] cycloaddition with phenylmethylketene. Lastly, the borata-benzofulvene system proved suitable as a ligand in metallocene chemistry. 2

1 Kohrt, S.; Dachwitz, S.; Daniliuc, C. G.; Kehr, G.; Erker, G. Dalton Trans. 2015,

44, 21032–21040.

2 Kohrt, S.; Daniliuc, C. G.; Wibbeling, B.; Kehr, G.; Erker, G. Manuscript in

preparation.

40

Poster 16

Metal-Ligand Cooperative Acitivation of Silanes in

PCcarbeneP Nickel Complexes

LaPierre, Etienne,a Piers, Warren*a

aUniversity of Calgary, Department of Chemistry, 2500 University Drive NW,

Calgary, AB, T2N 1N4


Recently there has been a push to impart nobel metal reactivity in base metal systems through ligand design.1 One approach to this is metal-ligand cooperation.2 Recently the Piers group reported a PCcarbeneP nickel carbene compound capable of activating a variety of small molecules, including ammonia, water and silanes.3,4 A mechanistic study showed that activation of silanes proceeded through a 2+2 mechanism, and

not oxidative addition, the typical activation pathway for late transition metals. Methods for incorporating of this activation in catalytic hydrosilylation are currently being investigated.

1Chirik, P. J.; Wieghardt, K. Science 2010, 327 (5967), 794–795.

2 Khusnutdinova, J. R.; Milstein, D. Angew. Chemie Int. Ed. 2015, 54 (42),

12236–12273.

3 Gutsulyak, D. V; Piers, W. E.; Borau-Garcia, J.; Parvez, M. J. Am. Chem. Soc.

2013, 135 (32), 11776–11779.

4 LaPierre, E. A.; Piers, W.; Spasyuk, D. M.; Bi, D. W. Chem. Commun. 2015

DOI: 10.1039/C5CC09349J.

41

Poster 17

Practical Terpyridine Cobalt Pre-Catalysts for Arene C-HBorylation

Nadia G. Leonard, Paul J. Chirik*Department of Chemistry, Princeton University, Princeton, NJ 08544,

United Statese-mail: [email protected]

The ubiquity of carbon-hydrogen bonds in organic molecules makes them attractive targets from which to build molecular complexity. The direct, selective functionalization of C-H bonds to form organoboronates is an indispensible tool in organic synthesis, due to the versatility of the resulting C-B bond. The use of precious metal catalysts dominates these transformations because of the ease of use,high activity and robustness of the catalyst precursors. Our laboratoryis interested in the development of operationally simple catalysts that rely on earth-abundant transition metals such as iron, cobalt, and nickel. Inexpensive, easily synthesized, and bench-stable terpyridine cobalt carboxylate complexes have been discovered that are readily activated in situ by substrate to catalytically borylate arene C-H bonds. My poster will focus on the synthesis, optimization, and scope of these complexes for catalytic C-B bond formation. Catalyst deactivation pathways and the consequences of the unique electron structures of first row transition metals will also be presented

N

N

NCo

O

Ar

O

OAcH 5 mol% [Co]B2Pin2, LiOMe

80 ºC, neat

Rn

BPinRn

Bench-Stable

Substrate-Activated

42

Poster 18

Practical Terpyridine Cobalt Pre-Catalysts for Arene C-HBorylation

Nadia G. Leonard, Paul J. Chirik*Department of Chemistry, Princeton University, Princeton, NJ 08544,

United Statese-mail: [email protected]

The ubiquity of carbon-hydrogen bonds in organic molecules makes them attractive targets from which to build molecular complexity. The direct, selective functionalization of C-H bonds to form organoboronates is an indispensible tool in organic synthesis, due to the versatility of the resulting C-B bond. The use of precious metal catalysts dominates these transformations because of the ease of use,high activity and robustness of the catalyst precursors. Our laboratoryis interested in the development of operationally simple catalysts that rely on earth-abundant transition metals such as iron, cobalt, and nickel. Inexpensive, easily synthesized, and bench-stable terpyridine cobalt carboxylate complexes have been discovered that are readily activated in situ by substrate to catalytically borylate arene C-H bonds. My poster will focus on the synthesis, optimization, and scope of these complexes for catalytic C-B bond formation. Catalyst deactivation pathways and the consequences of the unique electron structures of first row transition metals will also be presented

N

N

NCo

O

Ar

O

OAcH 5 mol% [Co]B2Pin2, LiOMe

80 ºC, neat

Rn

BPinRn

Bench-Stable

Substrate-Activated

Heterogenization of molecular Pd-NHC catalysts for

continuous flow processes

Martínez Albertoa Godard Cyril*a, Claver Carmen*a

aDepartament de Química Física i Inorgànica, Universitat Rovira i Virgili,

Tarragona, Spain.


A strategy for the immobilisation of Pd-NHC complexes onto inorganic solids is described.1 Based on literature precedents2,an original methodology is presented for the introduction of different functionalities into the framework of IMes and IPr salt precursors. 3 The resulting heterogenized catalysts were applied in C-C bond formation processes such as Suzuki-Miyaura, Heck and Sonogashira as well as in selective

alkyne semihydrogenations.Results will be described and discussed in terms of catalytic activity, selectivity and recyclability both in batch and in continuous flow along with stability issues.

1 a) Heterogenized homogeneous catalysts for fine chemicals production, P. Barbaro,

F. Liguori. Springer, 2010 b) H. Zhou, Y. M. Wang, W. Z. Zhang, J. P. Qu, X. B. Lu,

Green Chem. 2011, 13, 644-650; c) A. Martínez, J.L. Krinsky, I. Peñafiel, S. Castillón,

K. Loponov, A. Lapkin, C. Godard, C. Claver, Catal. Sci. Tech. 2014, 5, 310-319.

2 S. Leuthäußer, D. Schwarz, H. Plenio, Chem. Eur. J. 2007, 13, 7195-7203.

3 J.L. Krinsky, A. Martinez, C. Godard, S. Castillon, C. Claver, Adv. Synth. Catal.

2014, 356, 460-474.

43

Poster 19

Synthesis of Adipic Acid, 1,6-Hexanediamine and1,6-Hexanediol via Double n-Selective Hydroformylation of

1,3-ButadieneJaroslaw Mormula, Jan Breitenfelda, Oliver Trappa,b, Rocco

Pacielloc, Thomas Schauba,c* and Peter Hofmannb

a Catalysis Research Laboratory (CaRLa), Im Neuenheimer Feld 584,

D-69120, Heidelberg, Germany;

b Organisch-Chemisches Institut, University of Heidelberg, Im Neuenheimer

Feld 270, D-69120 Heidelberg, Germany

c BASF SE, Carl-Bosch-Strasse 38, D-67056 Ludwigshafen, Germany


A method for the synthesis of the industrially relevant monomers adipic acid, 1,6 hexanediol and 1,6-hexanediamine via isomerizing hydroformylation of 1,3-butadiene is described. The aldehyde intermediates are protected in situ as acetals to avoid hydrogenation to pentanal. Adipic aldehyde diacetal is obtained in good yields and first examples for the conversion towards adipic acid, 1,6-hexanediol and 1,6-hexanediamine are shown.1

1 Mormul, J.; Breitenfeld, J.; Trapp O.; Paciello R.; Schaub T.; Hofmann, P.

submitted

44

Poster 20

Easily accessible heterodinuclear bis(NAC)-

bridged gold(I)-palladium(II) complexes

Florian F. Mulks,a A. Stephen K. Hashmi*a

aOrganisch-Chemisches Institut, Ruprecht-Karls Universität Heidelberg, Im

Neuenheimer Feld 270, 69120 Heidelberg


We developed a wide range of NAC (N-acyclic carbene)complexes available by nucleophilic attack of amines to metal-coordinated isonitriles.1

Most aromatic amines are not sufficiently nucleophilic to attack

Au(I) isonitriles, therefore they can easily be introduced as additional functional group, which will react with Pd(II) isonitriles to the corresponding heterodinuclear complex.Protection groups enable the synthesis with aliphatic bridgesas well. This way the scope of our robust and easily applicable synthesis strategy is expanded by heterodinuclear complexes.

1 For early examples see: (a) A. S. K. Hashmi, C. Lothschütz et al., Adv. Synth.

Catal., 2010, 352, 1315-1337; (b) A. S. K. Hashmi, T. Hengst et al., Adv. Synth.

Catal., 2010, 352, 3001-3012.

45

Poster 21

Ammonia Triphos Derivatives and Diphosphines as Ligands in the Ruthenium-Catalysed Alcohol Amination with NH3

Naohisa Nakagawa,a Eric J. Derrah,a Mathias Schelwies,b

Frank Rominger,c Oliver Trappc and Thomas Schaub*a,b

aCaRLa – Catalysis Research Laboratory, Heidelberg, Germany; bSynthesis & Homogeneous Catalysis, Carl-Bosch-Strasse 38, BASF SE; cOrganisch-

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


Ruthenium catalysts have been reported to undergo the selective alcohol amination of NH3 to provide primary amines. We previously reported that a ruthenium-triphos complex is highly active for the mono-alkylation of NH3 with primary alcohols. In order to gain an insight how variations of the triphos scaffold influence the ruthenium-catalysed amination of alcohols with NH3, we synthesized and evaluated ruthenium-tridentate ligand complexes. Our approach was to alter the coordination sphere of triphos-type Ru-complexes in order to change the selectivities in the corresponding amination reactions.

46

Poster 22

Ammonia Triphos Derivatives and Diphosphines as Ligands in the Ruthenium-Catalysed Alcohol Amination with NH3

Naohisa Nakagawa,a Eric J. Derrah,a Mathias Schelwies,b

Frank Rominger,c Oliver Trappc and Thomas Schaub*a,b

aCaRLa – Catalysis Research Laboratory, Heidelberg, Germany; bSynthesis & Homogeneous Catalysis, Carl-Bosch-Strasse 38, BASF SE; cOrganisch-

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


Ruthenium catalysts have been reported to undergo the selective alcohol amination of NH3 to provide primary amines. We previously reported that a ruthenium-triphos complex is highly active for the mono-alkylation of NH3 with primary alcohols. In order to gain an insight how variations of the triphos scaffold influence the ruthenium-catalysed amination of alcohols with NH3, we synthesized and evaluated ruthenium-tridentate ligand complexes. Our approach was to alter the coordination sphere of triphos-type Ru-complexes in order to change the selectivities in the corresponding amination reactions.

Ni-catalyzed Carboxylation of Alkynes: Development of a

novel reductive system employing alcohol and CO2

Masaki Nakajima,a Xueqiang Wang,a Ruben Martina,b

a Institute of Chemical Research of Catalonia (ICIQ), Av. Països Catalans 16,

43007, Tarragona, Spain

b Catalan Institution for Research and Advanced Studies (ICREA), Passeig

Lluïs Companys, 23, 08010, Barcelona, Spain


Recently, the groups of Ma and Tsuji reported a syn-selective Hydrocarboxylation of alkynes employing CO2.1) However, their method is characterized through lack of regiocontrol or the usage of pyrophoric Et2Zn. Herein, we report a Ni-catalyzed divergent Hydrocarboxylation strategy en route to acrylic acids

furnishing high levels of selectivity.2) The overall carboxylation process is mild, whereby alcohol is introduced as a novel hydrogen source in the hydrocarboxylation event.

1 a) Li, S.; Yuan, W.; Ma, S. Angew. Chem. Int. Ed. 2011, 50, 2578; b)

Fujihara, T.; Xu, T.; Semba, K.; Terao, J.; Tsuji, Y. Angew. Chem. Int. Ed. 2011,

50, 523. 2 Wang, X.; Nakajima, M.; Martin, R. J. Am. Chem. Soc. 2015, 137,

8924.

47

Poster 23

Iridium catalysed dehydrocoupling of primary

phosphine-borane adducts

Paul Ursula,a Radius Udo*a

aInstitut für Anorganische Chemie, Julius-Maximilians-Universität Würzburg,

Am Hubland, D-97074 Würzburg


Iridium complexes bearing bis(phosphinite) pincer ligands like tBuPOCOP (3-C6H3-1,3-OPtBu2) have shown unique activity in the homogeneous dehydrogenation of various substrates such as alkanes and amine-boranes.1 We have investigated the thermal dehydrocoupling of phosphine-borane adducts of the

type ArPH2·BH3 in solution to yield poly(phosphinoboranes). Iridium bis(phosphinite) pincer complexes proved to be active

(pre)catalysts for this purpose.

Furthermore, to gain some insight into the mechanism of this reaction we studied the reactivity of the respective pincer complexes towards primary phosphines and boranes.2

1 Choi, J.; Roy MacArthur, A. H.; Brookhart, M.; Goldman, A. S. Chem. Rev.

2011, 111, 1761-1779; 2 Arnold, N.; Mozo, S.; Paul, U.; Radius, U.;

Braunschweig, H. Organometallics 2015, 34, 5709-5715.

48

Poster 24

Palladium-Catalyzed N-Alkylation

Peacock David,a Hartwig John*a

aUniversity of California - Berkeley


We report a thermal, palladium-catalyzed coupling of benzophenone imines with unactivated alkyl bromides to produce protected primary amines. In the presence of (Cy2t-BuP)2Pd0 and Cs2CO3, secondary and tertiary alkyl bromides react with benzophenone imine derivatives to form N-alkyl imines. The palladium-catalyzed coupling of secondary alkyl halides is a rare process, due to the slow oxidative

addition to form secondary alkylpalladium species, and mechanistic studies suggest that this amination of secondary alkyl bromides occurs by a reversible reaction with the palladium catalyst to form a free alkyl radical. The intermediacyof an alkyl radical allows this method to be extended to theintermolecular carboamination of an alkene.

49

Poster 25

New Applications of Chiral Phosphine-Phosphite Ligands

in Transition Metal Catalysis

Martin Reiher, Hans-Günther Schmalz*Department of Chemistry, University of Cologne, Germany


Recently, a modular synthesis of chiral phosphine-phosphite ligands of type 1 was developed in our group.1 These ligands proved to be highly useful in various asymmetric transition metal catalyzed C-C bond-forming transformations such as hydro-cyanation2 and hydro-vinylation.

Latest results concerning (1) the use of defined air-stable Cu-complexes of such ligands in 1,4-additions of Grignard reagents to enones and (2) Rh-catalysed transferhydro-formylations will be reported.

[1] M. Dindaroğlu, A. Falk, H.-G. Schmalz Synthesis 2013, 45, 527-535.

[2] A. Falk, A.-L. Göderz, H.-G. Schmalz Angew. Chem. Int. Ed. 2012, 52, 5,

1576-1580.

[3] S. Movahhed, J. Westphal, H.-G. Schmalz, unpublished results.

50

Poster 26

Enantioselective Allylic Substitutions Catalyzed by

Iridium/(P,olefin) Complexes: Characterization of

Intermediates in the Catalytic Cycle

Simon L. Rössler,a Simon Krautwald,a Erick M. Carreira*a

aLaboratorium für Organische Chemie, ETH Zürich, Switzerland


The Iridium/(P,olefin) catalyst system developed in our laboratory has been used extensively for the substitution of branched, racemic allylic alcohols with a variety of nucleophiles to afford products with high stereo- and regioselectivity.1 We now report isolation and characterization of iridium complexes

that are kinetically competent to be intermediates in these catalytic processes. Crystal structures of several intermediates and a resting state give mechanistic insights. In addition, acatalyst deactivation pathway was identified enabling optimization of in situ catalyst generation.

1 Lafrance, M.; Roggen, M.; Carreira, E.M. Angew. Chem. Int. Ed. 2012, 51,

3470-3473. Krautwald, S.; Sarlah, D.; Schafroth, M.A.; Carreira, E.M. Science

2013, 340, 1065-1068. Hamilton, J.Y.; Hauser, N.; Sarlah, D.; Carreira, E.M.

Angew. Chem. Int. Ed. 2014, 53, 10759-10762.

51

Poster 27

Rhodium(I)-Catalyzed Oxygenative [2+2] Cycloaddition of

Terminal Alkynes with Imines for the Synthesis of

-Lactams

Sang Weon Roh, Insu Kim, Dong Gil Lee, and Chulbom Lee*

Department of Chemistry, College of Natural Sciences,

Seoul National University, Seoul 151-747, Korea


Transition metal vinylidene complexes are useful catalytic

intermediates in a variety of reactions of terminal alkynes.

When oxygenated, these metal-unsaturated carbenes can be

converted to metalloketene species. In an ongoing effort to

utilize this vinylidene-to-ketene process, we discovered that the

ketene can undergo a Staudinger reaction with imines to give

-lactam products. Herein, we present our results of the

Rh(I)-vinylidene mediated oxygenative [2+2] cycloaddition of

terminal alkynes with various imines that gives -lactam

products in good to excellent yields.

52

Poster 28

Enantioselectivity Through Non-Covalent Interaction

Jan Felix Scholtes, Oliver Trapp*Organisch-Chemisches Institut, Ruprecht-Karls-Universität Heidelberg

Im Neuenheimer Feld 270, 69120 Heidelberg


Stereodynamic biphenyl ligands have shown to be a powerfultool in enantioselective catalysis when combined with a method to affect their stereochemical ratio. 1-3

A novel bisphosphine ligand is being presented that featureschiral interaction sites and shows intriguing conformational behavior in solution which can be influenced through non-covalent ligand-solute bonding. Additionally, these interactions affect the ligand’s diastereomeric ratio, which can

be utilized to generate an enantioselective hydrogenation catalyst.

1 Aikawa, K.; Mikami, K. Chem. Commun. 2012, 48, 11050-11069.

2 Storch, G.; Trapp, O. Angew. Chem. Int. Ed. 2015, 54, 3580-3586.

3 Storch, G.; Siebert, M.; Rominger, F.; Trapp, O. Chem. Commun 2015, 51,

15665-15668.hjg

53

Poster 29

Highly Active Dicopper CuAAC “Click” Catalysts

Anne L. Schöffler,a Bernd F. Straub*a

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

270, D-69120 Heidelberg, Germany; e-mail: [email protected]

The copper-catalyzed azide-alkyne cycloaddition (CuAAC) provides facile access to 1,4-disubstituted 1,2,3-triazoles. 1

Dinuclear copper(I) complexes with tailor-made N-heterocyclic carbene ancillary ligands and labile sacrificial ligands featurevery high catalytic activity in this “Click ” reaction.2, 3

1 Berg, R., Straub, B. F.; Beilstein J. Org. Chem. 2013, 9, 2715-2750.

2 Berg, R., Straub, J.; Schreiner, E.; Mader, S.; Rominger, F.; Straub, B. F.; Adv.

Synth. Catal. 2012, 354, 3445-3450.

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

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

54

Poster 30

Backbonding and Agostics in Coinage Metal Carbenes

Matthias W. Hussong,a Frank Rominger, Bernd F. Straub*a

aOrganisch-Chemisches Institut, Universität Heidelberg, Im Neuenheimer Feld

270, D-69120 Heidelberg, Germany ; e-mail: [email protected]

X-ray diffraction analyses of sterically shielded coinage metal dimesitylcarbene salts provide evidence for significant back-bonding in IPr** gold complexes1 and for marginal or small backbonding in the isostructural silver analogue.2 The “work-horse” IPr complex establishes a weak, but unprecedented,agostic interaction at gold both structurally and energetically.3

1 Hussong, M. W.; Rominger, F.; Krämer, P.; Straub, B. F. Angew. Chem. 2014,

126, 9526-9529; Angew. Chem. Int. Ed. 2014, 53, 9372-9375.

2 Hussong, M. W.; Hoffmeister, W. T.; Rominger, F.; Straub, B. F. Angew. Chem.

2015, 127, 10331-10335; Angew. Chem. Int. Ed. 2015, 54, 10472-10476.

3 Hussong, M. W.; Rominger, F.; Straub, B. F. manuscript submitted.

55

Poster 31

Extending N-heterocyclic carbene ligands into

the third dimension: A new type of hybrid

cyclophosph(III)azane/NHC system

Vladislav Vasilenko,a Torsten Roth,a

Dominic Wright,*b and Lutz H. Gade*a

aAnorganisch-Chemisches Institut, Universität Heidelberg, Germany bChemistry Department, Cambridge University, United Kingdom

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

A simple, “click” synthetic approach to a new type of hybrid cyclophosph(III)azane/NHC system is described. The new ligand is structurally rigid, a strong σ-donor and can coordinate additional metal centers using the P2N2 phosphorus-atoms.The orientation of the phosphazane ring unit perpendicular to the binding site of the NHC provides an unprecedented architecture for modifying the electronic and steric character of

these carbenes. Importantly, the flat spatial arrangement of conventional NHCs, often described as fence-like, is extended into the third dimension in our new system.

56

Poster 32

Ruthenium(II) Catalyzed Oxidative C–H Functionalizations with Oxygen as the Sole Oxidant

Svenja Warratz,a Christoph Kornhaaß,a Alexander Bechtoldt,a Lutz Ackermanna

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

Tammannstraße 2, 37077 Göttingen, Germany


Ruthenium(II)-catalyzed oxidative functionalizations of C–H bonds are powerful tools for the step-economical synthesis of bioactive heterocycles.1 Recently, we developed ruthenium-catalyzed oxidative alkyne2a and alkene annulations2b with molecular oxygen as a cheap and environmentally benign oxidant, thereby avoiding the formation of undesired metal-containing by-products.2 Thus, ruthenium(II) biscarboxylates set the stage for the expedient synthesis of isocoumarins and phthalides from easily

accessible, yet weakly coordinating benzoic acids.

1 Ackermann, L. Acc. Chem. Res. 2014, 47, 281-295. 2 (a) Warratz, S.; Kornhaaß, C.; Cajaraville, A.; Niepötter, B.; Stalke, D.;

Ackermann, L. Angew. Chem. Int. Ed. 2015, 54, 5513-5517. (b) Bechtoldt, A.;

Tirler, C.; Raghuvanshi, K.; Warratz, S.; Kornhaaß, C.; Ackermann; L. Angew.

Chem. Int. Ed. 2016, 55, 264-267.

57

Poster 33

First Crystal Structures of Reactive Rhodium Carbenoids C. Werlé,a R. Goddard,a P. Philipps,a C. Farès,a A. Fürstner*a a

Max-Planck-Institut für Kohlenforschung, D-45470 Mülheim/Ruhr, Germany


Dirhodium carbenoids have gained eminent importance in (asymmetric) synthesis and catalysis.1 As a consequence of their exceptional reactivity, these intermediates have long defied direct inspection. Only recently have Davies and co-workers managed to characterize a push-pull dirhodium carbene by NMR, EXAFS, and optical spectroscopy.2 Here we present the first crystal structures of reactive dinuclear Rh(II) and mononuclear Rh(III) carbenoids,3 which are the most commonly postulated intermediates in this field.Furthermore we unveil that dirhodium carbenoids undergo facile

carbene transfer to Au(I) through a formal transmetalation, opening anew entry into gold carbene complexes that cannot easily be made otherwise. This series provides an unprecedentedly close look at representative members of these families and reveals many conformational details which could hitherto only be inferred from indirect evidence and/or in silico data.

1 Evans P. A. Ed. Modern Rhodium Catalyzed Organic Reactions, Wiley-VCH, 2005.2 Kornecki K. P., Briones J. F., Boyarskikh Y., Fullilove F., Autschbach J., Schrote K. E.,

Lancaster K. M., Davies H. M. L., Berry J. F. Science 2013, 342, 351-354.

3 a) Werlé, C.; Goddard, R.; Fürstner, A. Angew. Chem. Int. Ed. 2015, 54,

15452-15456. b) Werlé, C.; Goddard, R.; Philipps P.; Farès C.; Fürstner, A. [Manuscript

submitted 21.12.15].

58

Poster 34

Palladium-Catalyzed Fluorination of Vinyl Triflates

Yuxuan Ye,a Stephen L. Buchwald*a

aDepartment of Chemistry, Massachusetts Institute of Technology, Cambridge,

Massachusetts 02139, United States


A Pd-catalyzed nucleophilic fluorination of vinyl triflates employing a new biarylphosphine ligand has been developedfor the convenient synthesis of fluoroalkenes.1 This catalytic fluorination exhibited a broad substrate scope with respect to both cyclic and acyclic vinyl triflates. Notably, the reaction proceeded with minimal formation of the corresponding reduction products, thereby greatly facilitating the purification

of these valuable fluorinated compounds. In particular, the use of substoichiometric amount of TESCF3 proved to be critical, leading to significantly improved regioselectivities2 for the current fluorination process.

1 (1) Sather, A. C.; Lee, H. G.; Rose, V. Y. D. L.; Yang, Y.; Müller, P.; Buchwald,

S. L. J. Am. Chem. Soc. 2015, 137, 13433 (2) Watson, D.A.; Su, M.;

Teverovskiy, G.; Zhang, Y.; García-Fortanet, J.; Kinzel, T.; Buchwald, S.L.

Science 2009, 325, 1661

2 For mechanistic studies of regioisomer formation: Milner, P. J.; Kinzel, T.;

Zhang, Y.; Buchwald, S. L. J. Am. Chem. Soc. 2014, 26, 2183

59

Poster 35

Peter Comba Universität Heidelberg Anorganisch-Chemisches Institut Im Neuenheimer Feld 270 69120 Heidelberg Germany [email protected]

Guy Lloyd-Jones School of Chemistry Forbes Professor of Organic Chemistry Joseph Black Building, West Mains Road EH9 3JJ Edinburgh UK [email protected]

Scott J. Miller Yale University Department of Chemistry CT 06520 New Haven USA [email protected]

Magnus Rueping RWTH Aachen University Institute of Organic Chemistry Landoltweg 1 52074 Aachen Germany [email protected]

Henrique Teles BASF, SE, GCS/X 67056 Ludwigshafen Germany [email protected]

Aiwen Lei Wuhan University College of Chemistry and Molecular Sciences 430072 Wuhan China [email protected]

Todd B. Marder Institut für Anorganische Chemie Am Hubland 97074 Würzburg Germany [email protected]

Tobias Ritter Max-Planck-Institut für Kohlenforschung Kaiser-Wilhelm-Platz 1 45470 Mühlheim/Ruhr Germany [email protected]

Mark Saeys Ghent University Laboratory for Chemical Technology Technologiepark 914 9052 Gent Belgium [email protected]

Lecturers

60

Midori Akiyama University of Tokyo Department of Chemistry and Biotechnology 7-3-1 Hongo, Bunkyo-ku 113-8656 Tokyo Japan [email protected]

Lena Daumann Universität Heidelberg Anorganisch-Chemisches Institut Im Neuenheimer Feld 270 69120 Heidelberg Germany [email protected]

Alexandre Dunlop-Briere Catalysis Research Laboratory (CaRLa) Im Neuenheimer Feld 584 69120 Heidelberg Germany [email protected]

Maximilian Ganiek Ludwig-Maximilians-Universität München Butenandtstr. 5-13 81377 München Germany [email protected]

Jennifer Griffin University of Illinois Department of Chemistry Urbana-Champaign Illinois USA [email protected]

Steven Banik Harvard University Department of Chemistry and Chemical Biology Harvard USA [email protected]

Nicklas Deibl University of Bayreuth Inorganic Chemistry II (Catalyst Design) 95440 Bayreuth Germany [email protected]

Juan Gallardo Catalysis Research Laboratory (CaRLa) Im Neuenheimer Feld 584 69120 Heidelberg Germany [email protected]

Nicolas Germain Catalysis Research Laboratory (CaRLa) Im Neuenheimer Feld 584 69120 Heidelberg Germany [email protected]

Dagmar Hackenberger TU Kaiserslautern Institut für Organische Chemie 67663 Kaiserslautern Germany [email protected]

Participants

61

Stephen Hashmi Universität Heidelberg Organisch-Chemisches Institut Im Neuenheimer Feld 270 69120 Heidelberg Germany [email protected]

Marko Hermsen BASF SE Carl-Bosch-Straße 38 67056 Ludwigshafen Germany [email protected]

Takahiro Iwamo International Research Center for Elements Science, Kyoto University Institute for Chemical Research 611-0011 Uji, Kyoto Japan [email protected]

Sonja Kohrt Universität Münster Organisch-Chemisches Institut Correnstra_e 40 48149 Münster Germany [email protected]

Nadia Leonard Princeton University Department of Chemistry NJ 08544 Princeton USA [email protected]

Alexander Haydl Albert-Ludwigs-Universität Freiburg Institut für Organische Chemie Hebelstraße 27 79085 Freiburg Germany [email protected]

Roman Honeker Westfälische Wilhelms-Universität Münster Organisch-Chemisches Institut Münster Germany [email protected]

Anna Kajetanowicz University of Warsaw Faculty of Chemistry, Biological and Chemical Research Centre _wirki i Wigury 101 02-089 Warsaw Poland [email protected]

Etienne LaPierre University of Calgary Department of Chemistry 2500 University Dr NW T2N1N4 Calgary, Alberta Canada [email protected]

Alberto Martinez Centre Tecnòlogic de la Química 43007 Tarragona Spain [email protected]

62

Jaroslaw Mormul Catalysis Research Laboratory (CaRLa) Im Neuenheimer Feld 584 69120 Heidelberg Germany [email protected]

Naohisa Nakagawa Catalysis Research Laboratory (CaRLa) Im Neuenheimer Feld 584 69120 Heidelberg Germany [email protected]

Ursula Paul Julius-Maximilians-Universität Würzburg Institut für Anorganische Chemie Am Hubland 97074 Würzburg Germany [email protected]

Martin Reiher University of Cologne Department of Chemistry Köln Germany [email protected]

Simon Rössler ETH Zürich Laboratorium für Organische Chemie 8093 Zürich Switzerland [email protected]

Florian Mulks Universität Heidelberg Organisch-Chemisches Institut Im Neuenheimer Feld 270 69120 Heidelberg Germany [email protected]

Masaki Nakajima Institute of Chemical Research of Catalonia (ICIQ) Av. Països Catalans 16 43007 Tarragona Spain [email protected]

Matt Peacock [email protected]

Sang Weon Roh Seoul National University Department of Chemistry, College Of Natural Sciences Seoul Korea [email protected]

Thomas Schaub BASF SE Carl-Bosch-Straße 38 67056 Ludwigshafen Germany [email protected]

Anna-Corina Schmidt Catalysis Research Laboratory (CaRLa) Im Neuenheimer Feld 584 69120 Heidelberg Germany [email protected]

63

Jan Scholtes Universität Heidelberg Organisch-Chemisches Institut Im Neuenheimer Feld 270 69120 Heidelberg Germany [email protected]

Oliver Trapp Universität Heidelberg Organisch-Chemisches Institut Im Neuenheimer Feld 270 69120 Heidelberg Germany [email protected]

Pablo Cabrera Ventura The University of Michigan Michigan USA [email protected]

Christophe Werlé Max-Planck Institut für Kohlenforschung Kaiser Wilhelm-Platz 1 45470 Mühlheim/Ruhr Germany [email protected]

Anne Schöffler Universität Heidelberg Organisch-Chemisches Institut Im Neuenheimer Feld 270 69120 Heidelberg Germany [email protected]

Bernd Straub Universität Heidelberg Organisch-Chemisches Institut Im Neuenheimer Feld 270 69120 Heidelberg Germany [email protected]

Vladislav Vasilenko Universität Heidelberg Anorganisch-Chemisches Institut Im Neuenheimer Feld 270 69120 Heidelberg Germany [email protected]

Svenja Warratz Georg-August-Universität Göttingen Institut für Organische und Biomolekulare Chemie Tammannstrasse 2 37077 Göttingen Germany [email protected]

Jedrzej Wysocki Catalysis Research Laboratory (CaRLa) Im Neuenheimer Feld 584 69120 Heidelberg Germany [email protected]

Yuxuan Ye Massachusetts Institute of Technology Massachusetts USA [email protected]

64

Your way to the conference venue:Deutsch Amerikanisches Institut (dai)

Sofienstrasse 1269115 Heidelberg

From Hotel Europäischer Hof

From Exzellenzhotel/Boardinghouse

distance: about 450 meters (5 minutes to walk)

Boarding-house

dai

daiHotel

Europäischer Hof

Exzellenz-hotel

65

LIST OF LUNCH VENUES

1MedocsWeekly changing lunch menu, burgers, steaks and saladsSofienstraße 7b • 69115 Heidelbergwww.medocs-cafe.de

2Galeria KaufhofBakery, kebab, pizza, Segafredo-bar, restaurant and caféBismarckplatz • 69115 Heidelbergwww.galeria-kaufhof.de/Heidelberg

3Café & Restaurant RossiDaily lunch offers in traditional coffee house ambianceRohrbacherstraße 4 • 69115 Heidelbergwww.caferossi.de

4Dean & David Well-priced, fresh salads, curries and soupsPoststraße 4 • 69115 Heidelbergwww.deananddavid.de

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5ThannerTraditional German Dishes, Swabian Pockets, Steaks and more. Bergheimerstraße 71a • 69115 Heidelbergwww.thanner.net

6

SHOPPING MALL • DAS CARRÉ

Tiger & Dragon’s Food CornerChinese dishes, daily lunch menu offersRohrbacherstraße 6-8 • 69115 Heidelbergwww.facebook.com/TigerDragon.HD/

mahlzeitAmerican Burges and traditional German CurrywurstRohrbacherstraße 6-8 • 69115 Heidelbergwww.mahlzeit-hd.de

Rich’n Greens100% Organic Salads, Burritos, Pasta and WrapsRohrbacherstraße 6-8 • 69115 Heidelbergwww.richngreens.de

PiratesPita, Kebab, Tarte Flambée,Cake, Coffee and more…Rohrbacherstraße 6-8 • 69115 Heidelbergwww.piratesheidelberg.com

7Urban KitchenPasta, Asian dishes, Steak, Burgers, Curries,…Poststraße 36/5 • 69115 Heidelbergwww.myurbankitchen.de

8Pasta BarPizza, Pasta, Salads and more…Neugasse 21 • 69117 Heidelbergwww.pastabar-hd.de

9Coffee NerdCoffee and moreRohrbacher Straße 9 • 69115 Heidelbergwww.coffeenerd.de

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9th carla winter school 2016 heidelberg

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