1112th CaRLa Winter School 2018 Winter School 2019 Heidelberg€¦ · Flash Poster Presentation (FPP) FPP FPP, BASF Career- Lunch Poster Prize Ceremony & Closing Remarks 12:00 –

11th CaRLa Winter School 2018

HeidelbergFebruary 18-23, 2018

Final Program

12th CaRLaWinter School 2019

HeidelbergFebruary 17-22, 2019

Final Program

Welcome to the 11th CaRLa Winter SchoolWelcome to the CaRLa Winter School in Heidelberg, presented by CaRLa, ourjoint 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 individualuse 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

Welcome to the 12th 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 scientifi c exchange between established and young researches in the fi eld of homogeneous catalysis. The conference takes place from February 17-22, 2019 at the German-American-Institute downtown Heidelberg, within walking distance to the old town.

Our scientifi c 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 fi rst part of each session will be a scientifi c 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 Wednesday (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 scientifi c 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!

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4

INDEX

Page

Welcome Message

Index

Program

Lecture Sessions

Poster Abstracts

List of Lecturers

List of Participants

Hotel Map

Map of Lunch Venues

3

4

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11

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5

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

SUNDAY • 17th February

Until 16:00 Arrival & Welcome Coffee

16:00 Opening Ceremony A. Stephen K. Hashmi

16:15 Introduction Winter School & CaRLa Thomas Schaub

17:00 Keynote Lecture BASF Henrique Teles

18:00 Light Dinner/Get Together

6

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

MONDAY • 18th February

09:00 Session Xumu Zhang

10:00 Coffee Break

10:15 Session Xumu Zhang

11:15 Coffee Break

11:30 Flash Poster Presentation


14:30 Session Dieter Vogt

15:30 Coffee Break

15:45 Session Dieter Vogt

16:45 Coffee Break


18:00 Light Dinner

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TUESDAY • 19th February

09:00 Session Olivier Baudoin

10:00 Coffee Break

10:15 Session Olivier Baudoin

11:15 Coffee Break

11:30 Flash Poster Presentation


14:30 Session Udo Radius

15:30 Coffee Break

15:45 Session Udo Radius

16:45 Coffee Break


18:00 Free Time

8

WEDNESDAY • 20th February

09:00 Session Troels Skrydstrup

10:00 Coffee Break

10:15 Session Troels Skrydstrup

11:15 Coffee Break

11:30 Flash Poster Presentation, BASF Career-Lunch

14:30 Session Burkhard König

15:30 Coffee Break

15:45 Session Burkhard König

16:45 Coffee Break


18:00 Light Dinner

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Lecture Sessions

THURSDAY • 21st February

09:00 Session Fumitoshi Kakiuchi

10:00 Coffee Break

10:15 Session Fumitoshi Kakiuchi

11:15 Flash Poster Presentation, Lunch and Poster Session

13:00 Excursion to BASF

18:00 Symposium Dinner(Kulturbrauerei, Leyergasse 6)

FRIDAY • 22nd February

09:00 Session A. Stephen K. Hashmi

10:00 Coffee Break

10:15 Session A. Stephen K. Hashmi

11:15 Coffee Break

11:30 Poster Prize Ceremony & Closing Remarks

12:00 Departure

10

Lecture Sessions

11

Oxidations – An Industrial PerspectiveHenrique Teles*

BASF SE, Process Research and Chemical Engineering

e-mail: [email protected]

The HPPO technology (Hydrogen Peroxide based Propylene Oxide) is one of the major breakthroughs in industrial chemistry and one of the very few completely new processes in the field of commodities and is now considered the most cost effective and most sustainable processes for the production of propylene oxide. BASF and Dow jointly developed the technology and now have three plants running with a total capacity of nearly 1 million tons per year. In this presentation I will explain how the weak points of an existing technology can be identified and how this knowledge, paired with new scientific discoveries has led to the development of a completely new HPPO process.

12

Practical Asymmetric Hydrogenation for Making Chiral Pharmaceuticals

Xumu ZhangDepartment of Chemistry, Southern University of Science and Technology, China


Dr. William Knowles, in his 2001 Nobel Lecture, describes his 1960s and 70s work in developing asymmetric hydrogenation catalysts. Now, 45 years later after the first commercial application of asymmetric catalysis, although major advances have been made (e.g.; Professor Noyori’s Nobel prize winning work in asymmetric hydrogenation), significant challenges remain. This presentation describes innovation in asymmetric hydrogenation catalysis from both an academic and industrial perspective. Having invented a catalyst that addresses an unmet need in asymmetric hydrogenation, many challenges remain before the catalyst provides an economic return. The knowledge gained and shortcomings recognized during scale-up and commercialization can lead to greatly improved ‘next generation’ catalysts.

This presentation highlights recent advances in our labs and the commercialization of many chiral phosphine ligands by Chiral Quest, Inc. The broad array of our chiral catalyst toolbox and their numerousapplications for a variety of functional group hydrogenations will be reviewed. The emphasis will be on the practical application of asymmetric hydrogenation to make chiral pharmaceutical in ton scale.

13

Concepts for Homogeneous Catalyst Immobilization and Recycling Dieter Vogt

Department of Industrial Chemistry and Chemical Process Development,

TU Dortmund, Emil-Figge-Strasse 66, 44227 Dortmund, Germany


Despite a number of striking advantages industrial applications of homogeneous catalytic processes are hampered by the intrinsic issue of catalyst separation and reuse. This lecture will present and discuss present and potential future approaches and put them in perspective. This will be done on the basis of practical examples from industry and from academic research.

14

Workshop on ligand effects in homogeneous catalysis and catalyst characterization

Dieter Vogt

Department of Industrial Chemistry and Chemical Process Development,

TU Dortmund, Emil-Figge-Strasse 66, 44227 Dortmund, Germany


Transition metal chemistry and the interplay of subtle effects of ligands are at the heart of homogeneous catalysis. Steric and electronic ligand effects, as well as coordination geometry and the conformations of catalysts influence to a large extend their activity, selectivity and stability. This subtle interplay will be discussed based on practical examples and problems to be solved.

15

Ring construction by Pd-catalyzed C(sp3)-H activationOlivier Baudoin

University of Basel, Department of Chemistry,

St. Johanns-Ring 19, 4056 Basel, Switzerland


Research efforts from our group in the past decade have focused on the functionalization of non-activated C(sp3)-H bonds using catalysis by palladium(0) complexes.1

This lecture will present some of the most recent aspects of this chemistry, including enantioselective reactions using different types of chiral catalysts,2 and applications in heterocycle3 and natural product synthesis.4

1O. Baudoin, Acc. Chem. Res. 2017, 50, 1114. 2 a) P. M. Holstein, M. Vogler, P. Larini,

G. Pilet, E. Clot, O. Baudoin, ACS Catal. 2015, 5, 4300; b) L. Yang, R. Melot, M.

Neuburger, O. Baudoin, Chem. Sci. 2017, 8, 1344; c) L. Yang, O. Baudoin, Angew.

Chem. Int. Ed. 2018, 57, 1394. 3 a) P. M. Holstein, D. Dailler, J. Vantourout, J. Shaya, A.

Millet, O. Baudoin, Angew. Chem. Int. Ed. 2016, 55, 2805; b) D. Dailler, R. Rocaboy, O.

Baudoin, Angew. Chem. Int. Ed. 2017, 56, 7218. 4D. Dailler, G. Danoun, O. Baudoin,

Angew. Chem. Int. Ed. 2015, 54, 4919.

16

Ring construction by Pd-catalyzed C(sp3)-H activation: tutorialOlivier Baudoin

University of Basel, Department of Chemistry,

St. Johanns-Ring 19, 4056 Basel, Switzerland


In the second part of the lecture, we will work on problem sets related to the lecture and to published work in the field.

17

Functionalization of Fluorinated Molecules by Transition-Metal-Mediated C−F Bond Activation

Udo RadiusInstitut für Anorganische Chemie, Julius-Maximilians-Universität Würzburg,

Am Hubland, 97074 Würzburg, Germany


Fluorinated organic compounds increasingly gain importance in numerous areas of chemistry and everyday life. Building blocks which contain fluorinated entities are of high significance in areas such as materials science, catalysis, medicine, and biochemistry. The main reason for this is because the reactivity and properties of molecules and ions can change dramatically in the presence of fluorinated moieties. Therefore, there is a growing demand for the development of unprecedented routes to access fluorinated molecules and building blocks, and even to design new scaffolds. One approach consists of a transition-metal-mediated synthesis, preferably by catalytic processes. This can involve fluorination reactions as well as the introduction of fluorinated functionalities, or alternatively, fluorinated compounds can be derivatized selectively at a transition-metal center to obtain the desired building blocks. For the latter, the activation of C-F bonds has emerged to be an interesting methodology. Poly- orperfluorinated molecules, which might be readily available byfluorination methods, can be derivatized in a unique way via thecleavage of a carbon-fluorine bond. This presentation coversdevelopments in the reaction of perfluorinated and partially fluorinatedsubstrates with transition metal complexes in stoichiometric andcatalytic processes.

This work was supported by the Deutsche Forschungsgemeinschaft (DFG)

and the Julius-Maximilians-Universität Würzburg.

18

On the Stability of N-Heterocyclic Carbenes: A Tutorial on Activation of Main-Group Element-Element Bonds and

Destruction of NHCsUdo Radius

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

Am Hubland, 97074 Würzburg, Germany


More than 25 years after the first report of the isolation and characterisation of a bottleable N-Heterocyclic Carbene (NHC), there is a widespread use of these molecules in organic and inorganic synthesis and catalysis. Since then, this class of compounds, as well as related molecules, e.g. cyclic (alkyl)(amino)carbenes (cAACs) and acyclic diaaminocarbenes (aDCs), have developed into an as yet unfinished success story par excellence in molecular chemistry. NHCs are usually regarded as stable spectator ligands or reagents, but the latest developments have shown that they are not always inert, innocent bystanders. In the last few years, more and more examples were reported of reactions of NHCs with main group elements and transition metals which resulted in the modification of the NHC core structure. Many of these reactions, for example, lead to ring opening or ring expansion with the formation of six-membered heterocyclic rings. The latter reaction involves an insertion of a heteroatom into the C-N bond and migration of hydrides, phenyl groups or boron-containing fragments to the carbene carbon atom. Furthermore, a fewclosely related NHC rearrangements were observed some decadesago. This tutorial gives a brief overview on NHCs and relatedmolecules in modern chemistry with an emphasis on the latestdevelopments concerning the stability of NHCs in main group elementand transition metal chemistry as well as catalysis.

This work was supported by the Deutsche Forschungsgemeinschaft (DFG)

and the Julius-Maximilians-Universität Würzburg.

19

New Directions in Transition Metal Catalyzed Carbonylation Chemistry

Troels Skrydstrup*Interdisciplinary Nanoscience Center, Department of Chemistry,

Aarhus University, Gustav Wieds Vej 15, 8000 Aarhus C, Denmark


We have earlier shown that the combination of palladium catalysis with carbon monoxide releasing molecules and the two-chamber reactor, COware®, provides a convenient and safe means for the discovery of new carbonylative couplings, which likewise can be exploited for carbon-isotope labeling of pharmaceutically relevant molecules.1,2 Herein, I provide a short overview of our latest findings in this area, but also discuss our efforts to develop viable Ni-catalyzed carbonylations with aliphatic substrates.3

1 a) Andersen, T.; Frederiksen, M.; Domino, K.; Skrydstrup, T. Angew. Chem. Int. Ed.

2016, 55, 10396. b) Lian, Z.; Nielsen, D.; Lindhardt, A.; Daasbjerg, K.; Skrydstrup, T.

Nat. Commun. 2016, 7, 13782. c) Domino, K.; Veryser, C.; Wahlqvist, B.; Gaardbo, C.;

Neumann, K.; Daasbjerg, K.; De Borggraeve W.; Skrydstrup, T. Angew. Chem. Int. Ed.

2018, 57, 6858.2 Friis, S.; Lindhardt, A.; Skrydstrup, T. Acc. Chem. Res. 2016, 49, 594.3 Andersen, T.; Donslund, A.; Neumann, K.; Skrydstrup, T. Angew. Chem. Int. Ed. 2018,

57, 800.

20

Retrosynthetic Analysis and Carbon MonoxideTroels Skrydstrup*

Interdisciplinary Nanoscience Center, Department of Chemistry,

Aarhus University, Gustav Wieds Vej 15, 8000 Aarhus C, Denmark


In this part of the course, we examine through assignments, how carbonylation chemistry can be implemented for constructing pharmaceutically relevant motifs applying retrosynthetic analysis. This includes in particular systems whereby it may not be directly obvious to pinpoint how carbon monoxide can be incorporated. As an example, Pd-catalyzed carbonylative -vinylation was exploited for the selective introduction of carbon-13 into the side chain of the blood cholesterol lowering drug, pitavistatin.1

1 Makarov, I.; Kuwahara, T.; Jusseau, X.; Ryu, I.; Lindhardt. A.; Skrydstrup, T.; J. Am.

Chem. Soc. 2015, 137, 14043.

21

Visible light photocatalysis IBurkhard König*

Faculty of Chemistry and Pharmacy, University of Regensburg, Germany


Visible light is a fantastic reagent for catalytic transformations: It is easily generated, selectively delivered within a reaction mixture, safe, and leaves no trace - even if applied in large excess. Photocatalysis utilizes the energy of light for chemical synthesis, as nature does in biological photosynthesis. Chemical photocatalysis has developed fast over the last 15 years and sophisticated methods for many transformations have been reported.1 We start with a quick refresher of some photophysical principles that are essential to design photocatalytic transformations. Next, we discuss photocatalytic oxidations,2 photocatalytic reductions3 and challenging cross-couplings with applications in synthesis.

1 L. Marzo, S. K. Pagire, O. Reiser, B. König, Angew. Chem. Int. Ed. 2018, 57,

10034.2 S. Das, P. Natarajan, B. König, Chem. Eur. J. 2017, 23, 18161.3 I. Ghosh, L. Marzo, A. Das, R. Shaikh, B. König, Acc. Chem. Res. 2016, 49,

1566.

22

Visible light photocatalysis II Burkhard König*

Faculty of Chemistry and Pharmacy, University of Regensburg, Germany


Dual catalysis combining photoredox and transition metal catalysts has recently let to amazing synthetic methods. We discuss key principles, recent applications in synthesis and the use of photo-nickel dual catalysis for the activation of carbon dioxide as building block in organic synthesis.1,2 We will then challenge our knowledge proposing improved reaction conditions and develop mechanistic proposals for photocatalytic transformations.

1 Q.-Y. Meng, S. Wang, B. König, Angew. Chem. Int. Ed. 2017, 56, 13426. 2 Q.-Y. Meng, S. Wang, G. S. Huff, B. König, J. Am. Chem. Soc. 2018, 140, 3198.

23

Transition-Metal-Catalyzed C–H Functionalization of Aromatic Compounds by Electrochemical Oxidation

Fumitoshi Kakiuchi*Department of Chemistry, Faculty of Science and Technology, Keio University, Japan


Transition-metal-catalyzed functionalization of C–H bonds has widely been studied in organic synthesis. Here, we describe convenient methods for introduction of functional groups on aromatic rings via transition-metal-catalyzed C–H bond cleavage and electrochemical oxidation.Combination of palladium-catalyzed ortho-selective aromatic C–H bond cleavage and halogenation with electrochemically generated X+ (X = Cl, Br, I) enables highly efficient, selective halogenations of aromatic compounds in a green-sustainable manner.1 Other C–H functionalization methods using electrochemical oxidation will also be discussed.

1 Kakiuchi F, Kochi T, Mutsutani H, Kobayashi N, Urano S, Sato, M, Nishiyama S,

Tanabe T: J. Am. Chem. Soc. 2009, 131: 11310-11311. Aiso H, Kochi T, Mutsutani H,

Tanabe T, Nishiyama S, Kakiuchi F: J. Org. Chem. 2012, 77, 7718-7724.2 Saito F, Aiso H, Kochi T, Kakiuchi F: Organometallics 2014, 33: 6704-6707. Kakiuchi,

F.; Kochi, T. Isr. J. Chem. 2017, 57, 10-11, 953-963.

24

Catalytic Functionalization via Unreactive Bond Cleavage Fumitoshi Kakiuchi*

Department of Chemistry, Faculty of Science and Technology, Keio University, Japan


Highly efficient catalytic alkylation of aromatic carbon–hydrogen bonds with alkenes was reported in 1993.1 This study showed that the use of weak coordination of heteroatom(s) to transiton-metal center is quite effective for selective cleavage of unreactive bonds. Since then, this chelation-assistance strategy has widely been used in a large number of catalytic functionalizations of unreactive bonds.2 This tutorial deals with fundamental aspects of transition-metal-catalyzed functionalization reactions via unreactive bond cleavages.3 We will also discuss details of reaction mechanisms such as mechanism of catalytic alkylation of C–H bond with alkenes.4

1 Murai, S.; Kakiuchi, F.; Sekine, S.; Tanaka, Y.; Kamatani, A.; Sonoda, M.; Chatani, N.

Nature 1993, 366, 529-531. Kakiuchi, F.; Murai, S. Acc. Chem. Res. 2002, 35, 826-834.2 Dong, Z.; Ren, Z.; Thompson, S. J.; Xu, Y.; Dong, G. Chem. Rev. 2017, 117, 9333-

9403.3 Kakiuchi, F.; Kochi, T.; Murai, S. Synlett 2014, 17, 2390-2414.4 Kakiuchi, F.; Kochi, T.; Mizushima, E.; Murai, S. J. Am. Chem. Soc. 2010, 132, 17741-

17750.

25

Poster Abstracts

26

Poster 1

CaRLa – The Catalysis Research LaboratoryA. Stephen K. Hashmi*a,b, 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.

27

Poster 2

Highly Enantioselective Iron-Catalyzed Reduction of Functionalized Ketones and Unprivileged Imines

Clemens K. Blasius, Vladislav Vasilenko, Lutz H. Gade* Anorganisch-Chemisches Institut, Ruprecht-Karls-Universität Heidelberg,

Im Neuenheimer Feld 270, 69120 Heidelberg, Germany


In recent years, many studies disclosed the potential of environmentally benign and earth-abundant 3d metals in enantioselective catalysis for the reduction of carbon-carbon and carbon-heteroatom multiple bonds.1 Despite the tremendous growth of this field, the majority of the presented catalytic systems is limited to simple diaryl, aryl alkyl and dialkyl ketones as the substrates, with more complex structures being explored only in selected cases.2 Herein, we present a molecularly defined iron alkyl complex (PhboxmiFeCH2SiMe3) as a catalyst for the enantioselective hydroboration of various functionalized ketones, providing access to chiral halohydrines, the respective oxaheterocycles and amino alcohols in excellent yields and enantioselectivities.3 Due to the high activity of the catalytic system, we were able to further extend our methodology to the reduction of unprivileged imines for the direct synthesis of -chiral amines.

1 (a) R. H. Morris, Chem. Soc. Rev. 2009, 38, 2282–2291; (b) P. J. Chirik, Acc. Chem.

Res. 2015, 48, 1687–1695. 2 (a) S. Zhou, S. Fleischer, K. Junge, S. Das, D. Addis, M. Beller, Angew. Chem. Int. Ed.

2010, 49, 8121–8125; (b) S. Smith, R. H. Morris, Synthesis 2015, 47, 1775–1779; (c) J.

Guo, J. Chen, Z. Lu, Chem. Commun. 2015, 51, 5725–5727. 3 C. K. Blasius, V. Vasilenko, L. H. Gade, Angew. Chem. Int. Ed. 2018, 57, 10231–

10235.

28

Poster 3

Ruthenium-catalyzed deaminative hydrogenation of nitriles to primary alcohols

Pilar Callejaa, István G. Molnár a, Martin Ernstb, A. Stephen K. Hashmia,c, Thomas Schauba,b

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

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

Germany.


Over the last years, extensive efforts have been devoted towards the development of new catalytic methods which allow the selective conversion of nitriles into a variety of functional groups, from carboxylic acids to amines.1 Herein we present the development of a high selective transformation for the direct conversion of aliphatic and aromatic nitriles into alcohols under relatively mild conditions, employing the commercially available RuHCl(CO)(PPh3)3 as catalyst.2

Remarkably, this operationally simple system features a broad functional group tolerance, leading to the corresponding products in high yields with NH3 as the sole by-product.

1 Selected reviews on nitrile reduction: a) Bagal, D. B.; Bhanage, B. M. Adv. Synth. Catal.

2015, 357, 883-900; b) Werkmeister, S.; Junge, K.; Beller, M. Org. Process Res. Dev.

2014, 18, 289-302.2 Molnár, I. G.; Calleja, P.; Ernst, M.; Hashmi, A. S. K.; Schaub, T. ChemCatChem. 2017,

9, 4175-4178.

29

Poster 3Poster 4

Synthesis of new exo-vinylene carbonates by carboxylative cyclization of propargylic alcohols using Ag (I) catalysts

Saumya Dabrala, Bilguun Bayarmagnaia, Marko Hermsenb, Jasmin Schießlc, Verena Mormulb, A. Stephen K. Hashmia,c, Thomas

Schaub*,a,b

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

b

69120 Heidelberg, Germany.

BASF SE, Synthesis & Homogeneous Catalysis, Carl-Bosch-Str. 38,67056 Ludwigshafen, Germany.

c Institute of Organic Chemistry, Heidelberg University, Im Neuenheimer Feld 270,

69120 Heidelberg, Germany.


The cyclization of unsaturated organic moieties via CO2 insertionrepresents an atom-economical approach for the synthesis of a range of exo-vinylene carbonate building blocks. These cyclization reactions have been particularly successful for the synthesis of substituted α-alkylidene cyclic carbonates using either precious transition-metals or by employing relatively harsh reaction conditions.[1] We report for the first time, the synthesis of new unsubstituted α-alkylidene cyclic carbonates in excellent yields under mild reaction conditions.

1 Kim, T.-J.; Kwon, K.-H.; Kwon, S.-C.; Baeg, J.-O.; Shim, S.-C.; J. Organomet. Chem.

1990, 389, 205-217.2 Bruneau, C.; Dixneuf, P. H. J. Mol. Catal. 1992, 74, 97-107.

30

Poster 4Poster 5

Direct Photoassisted α-Trifluoromethylation of Aromatic Ketones with Trifluoroacetic Anhydride (TFAA)

Somnath Dasa, A. Stephen K. Hashmi a,b, Thomas Schauba,c

aCatalysis Research Laboratory (CaRLa), INF 584, 69120 Heidelberg. bOrganisch-Chemisches Institut, Heidelberg University, INF 270, 69120 Heidelberg.

cBASF SE, Synthesis and Homogeneous Catalysis,67056 Ludwigshafen.

e-mail: [email protected].

We present here a method for the direct α-Trifluoromethylation of acetophenone derivatives by using trifluoroacetic anhydride (TFAA) as the trifluoromethyl source and pyridine-N-oxide (Py-O) as activator and oxidant under visible light irradiation.1,2 (Ru(bpy)3(PF6)2) wasemployed as the photocatalyst. Mechanistic investigation revealed the formation of vinyl trifluoroacetate as the key intermediate for this transformation.

CH3

O

R

O

RCF3

TFAA/Py-ORu(bpy)3(PF6)2

Blue light, MeCN, 65 °C

OCOCF3

RCF3

TFAA

Pyridine-N-oxide

Scheme1 Direct α-trifluoromethylation of acetophenone derivativesunder visible light irradiation.

1a) Beatty, J. W.; Douglas, J. J.; Cole, K. P.; Stephenson, C. R. J. Nat. Commun. 2015,

6, 7919; b) Beatty, J. W.; Douglas, J. J.; R. Miller, McAtee, R. C.; Cole, K. P.;

Stephenson, C. R. J. Chem 2016, 1, 456-472.2Das, S; Hashmi, A. S. K.; Schaub, T. Adv. Synth. Catal. 2018, in press.

31

Poster 5Poster 6

Nickel-Catalyzed Enantioselective Pyridone C-H Functionalizations Enabled by a Bulky

N-Heterocyclic Carbene LigandJohannes Diesel, M. Anastasiia Finogenova, Nicolai Cramer

LCSA, ISIC, EPFL, Lausanne, Switzerland


Cooperative Lewis acid/nickel(0)-catalysis and application of N-heterocyclic carbene ligands (NHCs) enables C-H activation andregioselective cyclization under formation of chiral annulated2-pyridones.1

Here, we introduce sterically demanding chiral NHCs with largemodulation opportunities, empowering the enantioselective C-Hfunctionalization of 2- and 4-pyridones.2 Their close relationship to theachiral privileged ligand IPr holds the promise of enabling furthercatalytic enantioselective transformations with a variety of transitionmetals.

1 (a) Tamura, R.; Yamada, Y.; Nakao, Y.; Hiyama, T. Angew. Chem. Int. Ed. 2012, 51,

5679. (b) Donets, P. A., Cramer. N. Angew. Chem. Int. Ed. 2015, 54, 633. 2 Diesel, J; Finogenova, A. M.; Cramer, N. J. Am. Chem. Soc. 2018, 140, 4489.

32

Poster 7

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

Tamal Ghosha, Maximilian Menchea,b, A. Stephen K. Hashmia,c,Ansgar Schäferb, Peter Combaa,d, Thomas Schaub*,a,e

a Catalysis Research Laboratory (CaRLa), INF 584, 69120 Heidelberg, Germany.b BASF SE, Quantum Chemistry and Molecular Simulation, Carl-Bosch-Str. 38,

67056 Ludwigshafen, Germany. c Institute of Organic Chemistry, Heidelberg

University, INF 270, 69120 Heidelberg, Germany. d Institute of Inorganic Chemistry,

Heidelberg University and Interdisciplinary Center for Scientific Computing (IWR),

INF 270, 69120 Heidelberg, Germany. e BASF SE, Synthesis and Homogenous

Catalysis, Carl-Bosch-Str. 38, 67056 Ludwigshafen, 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 a chiral [Ru((S,S)-f-binaphane)COHI(PPh3)] complex, which we identified as the most efficient catalyst in our investigation.1

1 J. Gallardo-Donaire, M. Hermsen, J. Wysocki, M. Ernst, F. Rominger, O. Trapp, A. S.

K. Hashmi, A. Schäfer, P. Comba, T. Schaub, J. Am. Chem. Soc. 2018, 140, 355-361.

33

Poster 7Poster 8

Rhodium-Catalyzed Enantioselective Decarboxylative Alkynylation of Allenes with Arylpropiolic Acids

Christian P. Grugel, Bernhard Breit* Institut für Organische Chemie

Albert-Ludwigs-Universität Freiburg, Albertstr. 21, 79014 Freiburg, Germany


Chiral 1,4-enynes constitute valuable and versatile intermediates for organic synthesis,1 mostly owing to the fact that they bear two different handles in direct vicinity to a stereogenic center that allow for selective further functionalization. However, their synthesis is commonly achieved by means of allylic substitution reactions employing pre-metalated alkyne nucleophiles, which are consequently accompanied by the generation of over-stoichiometric amounts of (salt) waste. To overcome this limitation, we herein report on a rhodium-catalyzed decarboxylative addition of arylpropiolic acids as terminal alkyne surrogates2 to allenes to construct chiral 1,4-enynes. The reaction proceeds with perfect chemo- and regioselectivity as well as excellent enantioselectivity releasing carbon dioxide as the sole byproduct. The mildness and overall utility of the developed protocol is exemplified bya broad substrate scope and functional group tolerance.3

1For selected examples on transformations of 1,4-enynes, see: a) Heffron, T. P.;

Jamison, T. F. Org. Lett. 2003, 5, 2339. b) Jacobson, M.; Redfern, R. E.; Jones, W. A.;

Aldridge, M. H. Science 1970, 170, 542. 2For a review on decarboxylative coupling reactions of propiolic acids, see: Park, K.;

Lee, S. RSC Adv. 2013, 3, 14165.3Grugel, C. P.; Breit, B. Org. Lett. 2018, 20, 1066.

34

Poster 8Poster 9

Synthesis of Transition Metal Complexes with a Four Membered Cyclic Bent Allene Ligand

Ludwig Hackl, Loung Phong Ho, Matthias Tamm Institut für Anorganische und Analytische Chemie, TU Braunschweig, Hagenring 30,

38106 Braunschweig, Germany


The performance of organometallic catalysts often depends on the properties of the employed ligand system. A type of ancillary ligand systems, exhibiting exceptional high donor strength, are cyclic bent allene (CBA) ligands. Despite their interesting properties, only very few examples have been reported over time.1 One of these ligands hasbeen used in an highly active olefin hydrogenation catalyst.2 We present a novel synthetic route to access transition metal complexes (e.g. gold, copper, rhodium, iridium, tungsten) bearing a CBA ligand, using the tetraamino substituted enyne 1, which can be synthesised by thermal dimerisation of bis(piperidyl)acetylene.

Scheme 1: Synthesis of CBA transition metal complexes.

1 e.g.: Melaimi, M.; Parameswaran, P.; Donnadieu, B.; Frenking, G.; Bertrand, G.

Angew. Chem. Int. Ed. 2009, 48, 4792−4795.2 Pranckevicius, C.; Fan, L.; Stephan, D. W J. Am. Chem. Soc. 2015, 137, 5582–5589.

35

Poster 10

Towards the Total Synthesis of Members of the Shearinine Family of Natural Products

Nicole Hauser, Michael Imhof, Leonardo J. Nannini, Carreira, Erick M.*

Laboratorium für Organische Chemie, ETH Zürich, 8093 Zürich, Switzerland


The shearinine natural products are indole terpenoids which have been isolated from a variety of different marine fungi during the last two decades.1 They exhibit an interesting pharmacological profile ranging from antiinsectan activity1a over blocking voltage- and calcium-activated potassium ion channels1b and anti-cancer activity1c to the inhibition of biofilm formation of C. albicans.2 Our synthetic approach relies on a number of transition metal-catalyzed transformations.

1 a) Belofsky, G. N.; Gloer, J. B.; Wicklow, D. T.; Dowd, P. F. Tetrahedron 1995, 51,

3959–3968. b) Xu, M.; Gessner, G.; Groth, I.; Lange, C.; Christner, A.; Bruhn, T.; Deng,

Z.; Li, X.; Heinemann, S. H.; Grabley, S.; Bringmann, G.; Sattler, I.; Lin, W. Tetrahedron

2007, 63, 435–444. c) Smetanina, O. F.; Kalinovsky, A. I.; Khudyakova, Y. V.; Pivkin, M.

V.; Dmitrenok, P. S.; Fedorov, S. N.; Ji, H.; Kwak, J.-Y.; Kuznetsova J. Nat. Prod. 2007,

70, 906–909. d) Basanta, D.; Michele, S.; Rainer, W.; Dieter, S. Chem. – Eur. J. 2018,

24, 4445–4452. 2 You, J.; Du, L.; King, J. B.; Hall, B. E.; Cichewicz, R. H. ACS Chem. Biol. 2013, 8, 840–

848.

36

Poster 11

Protodeboronation of Boronic Esters: A Mechanistic Investigation

Hannah L. D. Hayesa, Gary Noonanb, Guy. C. Lloyd-Jonesa

a School of Chemistry, University of Edinburgh, United KingdombAstraZeneca, Macclesfield


Boronic acids and boronic esters are indispensable building blocks in modern synthetic chemistry, frequently utilised to produce active ingredients for drugs and herbicides. Recent work in the Lloyd-Jones group has involved examination of the protodeboronation of a diverse range of arylboronic acids.1 The improved stability of boronic esters under anhydrous conditions2 is believed to be a consequence of the reduced Lewis acidity at the boron center.3 This project aims to investigate the impact of diols on the protodeboronation rate of boronic acids in addition to identifying whether boronic esters undergo direct protodeboronation or in fact protodeboronate via the boronic acid.

Potential mechanistic pathway

1 (a) P. A. Cox; A. G. Leach; A. D. Campbell and G. C. Lloyd-Jones, J. Am. Chem. Soc.,

2016, 138, 9145-9157; (b) P. A. Cox; M. Reid; A. G. Leach; A. D. Campbell; E. J. King

and G. C. Lloyd-Jones, J. Am. Chem. Soc., 2017, 139, 13156-131652 (a) D. W. Robbins and J. F. Hartwig Org. Lett., 2012, 14, 4266−4269; (b) L. Chen; H.

Francis and B.P. Carrow, ACS Catal. 2018, 8, 2989–29943 A. J. Lennox and G. C. Lloyd-Jones, Chem. Soc. Rev., 2014, 43, 412-443

37

Poster 10Poster 12

CO2-Chemistry @ CaRLa Chloe Johnsona, Nicolas Germaina, Simone Manzinia, Thomas

Schauba,b*aCaRLa, Im Neuenheimer Feld 584, D-69120 Heidelberg, Germany

bBASF SE, Synthesis & Homogeneous Catalysis, Carl-Bosch-Str. 38, D-67056

Ludwigshafen, Germany


Carbon dioxide is a cheap and abundant C1 building block andtherefore attractive for industrial use. In CaRLa, we targeted the direct synthesis of sodium acrylate from CO2 and ethylene as a “Dream Reaction” (Scheme a). This project has been developed in stages: from our initial report on the catalytic synthesis of acrylates using this carboxylative route, to the adaption of the system to a continuous process concept with turnover numbers of 200.1 In a second project, we demonstrated a straightforward, phosgene‐free synthesis of aromatic isocyanates and diisocyanates (polyurethane building blocks) using CO2 and anilines mediated by organotin derivatives (Scheme b).2

Sodium acrylate (a) and isocyanate (b) synthesis using CO2 as a C1

building block.

1 Manzini, S.; Cadu, A.; Schmidt, A.C.; Huguet, N.; Trapp, O.; Paciello, R.; Schaub, T.

ChemCatChem 2017, 9, 2769-2774.2 Germain, N.; Müller, I.; Hanauer, M.; Paciello, R.; Baumann, R.; Trapp, O.; Schaub,

T. ChemSusChem 2016, 9, 1586-1590.

38

Poster 11Poster 13

Regio- and Enantioselective Amination of Branched Allylic Acetates Bearing Linear Alkyl Groups

Seung Wook Kim, Michael J. Krische* University of Texas at Austin, Department of Chemistry (A5300), USA

AUSTIN, TX 78712-0165


Transition metal-catalyzed allylic substitution has emerged as a powerful method for stereoselective C-N bond formation. Chiral iridium-phosphoramidite complexes have proven especially effective as catalysts for regio- and enantioselective allylic amination, but are limited to ARYL-substituted π-allyl electrophiles. We have demonstrated that π-allyliridium C,O-benzoate complexes catalyze completely regio- and highly enantioselective aminations of diverse ALKYL-substituted allylic electrophiles. Mechanistic studies corroborate C-N bond formation via outer-sphere addition.

1 Meza, A. T.; Wurm, T.; Smith, L.; Kim, S. W.; Zbieg, J. R.; Stivala, C. E.; Krische, M. J.

J. Am. Chem. Soc. 2018, 140, 1275.2 Kim, S. W.; Schwartz, L. A.; Zbieg, J. R.; Stivala, C. E.; Krische, M. J. J. Am. Chem.

Soc., Article ASAP. DOI: 10.1021/jacs.8b12152.

39

Poster 14

Iron(II) catalyzed halogenation of unactivated alkanes Peter Comba, Saskia Krieg, Michael Schukin

Heidelberg University, Institute of Inorganic Chemistry, INF 270, 69120 Heidelberg, Germany


High-valent iron-oxo complexes have been in focus of research, since both enzymes as well as model complexes are known to catalyze a wide range of oxidation and halogenation reactions.1-3 The[(N2py2)Fe=O(Cl)]+ complex reported here has shown activity in both reactions mentioned above. The chlorination of substrates with high C-H bond strengths like cyclohexane is performed with high selectivity to the halogenated product (close to 100 % selectivity over hydroxylation). Interestingly, uncomplexed FeCl2 shows a similar selectivity and only slightly lower reactivity.

Chlorination of cyclohexane with the complex [(N2py2)Fe=O(Cl)]Cl and FeCl2.

1 Groves, J.T. J. Inorg. Biochem. 2006, 100, 434–447.2 Nam, W. Acc. Chem. Res. 2007, 40, 522–531.3 Comba, P.; Wunderlich, S. Chem. Eur. J. 2010, 7293–7299.

40

Poster 13Poster 15

A Greener Route to Amides Amit Kumar, David Milstein

Department of Organic chemistry, Weizmann Institute of Science, Rehovot, Israel


Amide bond formation is one of the most fundamental reactions in chemistry and biology and is of significant importance in the pharmaceutical industries. Conventional methods for the synthesis of amides involve reaction of amines with either carboxylic acids or their derivatives in presence of an activator thus generating stoichiometric amount of waste. An environmental benign and atom-economic synthesis of amides is therefore highly desirable. In 2007, we discovered the first dehydrogenative coupling of alcohols and amines to form amides using a ruthenium pincer catalyst.1 We now present the first example of base-metal-catalysed synthesis of amide bonds from the dehydrogenative coupling of cheap and easily available strating materials such as alcohols or esters or diols and amines.2,3 The reactions are catalysed by pincer complexes of earth abundant manganese (prectalysts 1 and 2) and form hydrogen gas as the sole byproduct, making the overall process atom economical, sustainable and environmentally benign.

1Gunanathan, C.; Ben-David, Y.; Milstein, D. Science 2007, 317, 790. 2Kumar, A.; Espinosa-Jalapa, N. A.; Leitus, G.; Diskin-Posner, Y. Avram. L.; Milstein, D. Angew. Chem., Int. Ed. 2017, 56, 14992. 3Espinosa-Jalapa, N. A.; Kumar, A.; Leitus, G.; Diskin-Posner, Y.; Milstein, D. J. Am. Chem. Soc. 2017, 139, 11722.

41

Poster 16

Asymmetric Allylic C–H Alkylation via Pd(II)/Sulfoxide-Oxazoline(SOX) Catalysis

Wei Liu, M. Christina WhiteUniversity of Illinois at Urbana-Champaign, USA


Asymmetric allylic C–H alkylation allows for the construction of C(sp3)–C(sp3) framework from inert C–H bonds with the concomitant establishment of stereochemistry. This report details the development of cis-sulfoxide-oxazoline (cis-ArSOX) ligands for Pd(II)-catalyzed asymmetric C–H alkylation of terminal olefins with a variety of synthetically versatile nucleophiles (e.g. α-nitroketones, β-ketoesters).The modular, tunable, and oxidatively stable cis-ArSOX scaffold is key to the broad scope and high enantioselectivity (37 examples, avg. >90% ee). From X-ray crystallographic analysis, the π-π interactionbetween the cis-substituents on the sulfoxide and oxazoline may contribute to the asymmetric induction. Pd(II)/cis-ArSOX is also able to effect the asymmetric alkylation of chiral aliphatic olefins, an unprecedented olefin class, with high reactivity and catalyst-controlled diastereoselectivity (avg. 10:1 d.r.). We anticipate that this new chiral ligand class will find use in other transition metal catalyzed processes that operate under oxidative conditions.

R1

H+ R1

OO2NOR2

cis-ArSOX

Pd(OAc)2

H

prochiral

*

>90% ee1 equiv.

SO

NOPdH

AcO OAccis-ArSOX

�-� interaction

MeOMeO OMe

Me

O

NH

43% overall yield, 91% eeprevious: 6% yield, 0% ee

O

OMeO2CMe

O

Et

Ph

cephalimysincore structure

N

O

Me

MeO

N

O

Me

MeOOtBuO2C

N

O

Me

MeOOtBuO2C

Pd(II)/(S,S)-ArSOXPd(II)/(R,R)-ArSOX

93% yield, 5:1 d.r.89% yield, 1:4 d.r.

Diastereoselective alkylation

42

Poster 17

3d Transition Metals for Asymmetric C–H Functionalizations Joachim Loup, Lutz Ackermann*

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

Göttingen, Tammannstraße 2, 37077 Göttingen, Germany


While significant progress in the direct functionalization of otherwise inert C–H bonds was realized with the aid of precious, toxic 4d and 5d transition metal catalysts, recent focus has shifted to their Earth-abundant and inexpensive 3d counterparts.1 However, enantioselective C–H transformations continue to heavily rely on noble transition metals, such as palladium, iridium and rhodium,2 with elusive reports on asymmetric C–H functionalizations with sustainable 3d metals. Within our program on non-toxic iron catalysis,3 we developed the first enantioselective iron-catalyzed C–H alkylation.4 Key to success was the design of novel meta-decorated NHC ligands. Moreover, we recently reported on the first asymmetric, aluminium-free, nickel-catalyzed hydroarylations of unactivated alkenes via C–H activation.5

1 P. Gandeepan, T. Müller, D. Zell, G. Cera, S. Warratz, L. Ackermann, Chem. Rev. 2019, DOI:10.1021/acs.chemrev.8b00507. 2 C. G. Newton, S.-G. Wang, C. C. Oliveira, N. Cramer, Chem. Rev. 2017, 117, 8908–8976. 3 G. Cera, L. Ackermann, Top. Curr. Chem. 2016, 374, 191–224. 4 J. Loup, D. Zell, J. C. A. Oliveira, H. Keil, D. Stalke, L. Ackermann, Angew. Chem. Int. Ed. 2017, 56, 14197–14201. 5 J. Loup, V. Müller, D. Ghorai, L. Ackermann, Angew. Chem. Int. Ed. 2019, DOI: 10.1002/anie.201813191.

43

Poster 16Poster 18

Cobalt-Catalyzed Acylation-Reactions of (Hetero)arylzinc Pivalates with Organic Thiopyridylester derivatives

Ferdinand H. Lutter, Lucie Grokenberger, Maximilian S. Hofmayer, Paul Knochel*

Department of Chemistry, Ludwig-Maximilians-Universität München,

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


The carbonyl group is a central motif in organic chemistry. The performance of acylation reactions using organometallic reagents represents a general access to various ketones. A major drawback of these reactions is a restricted chemoselectivity and the use of expensive or toxic transition-metal catalysts. Whereas acid chlorides are broadly available acylating agents, their preparation requires harsh conditions, and thus lowering the functional group tolerance. Alternatively, thioesters readily react with organozinc halides in the presence of a palladium catalyst.1 Recent advances have shown that solid arylzinc pivalates, displaying an enhanced stability towards moisture and air, are especially suited to undergo cobalt-catalyzed reactions.2 We have developed a new cobalt-catalyzed synthesis of a variety of polyfunctional ketones by the acylation of various S-pyridylesters with aryl- and heteroarylzinc pivalates.3

1 Tokuyama, H.; Yokoshima, S.; Yamashita, T.; Fukuyama T. Tetrahedron Lett. 1998,

39, 3189-3192. 2 Hammann, J. M.; Lutter, F. H.; Haas, D.; Knochel P. Angew. Chem. Int. Ed. 2017, 56,

1082–1086. 3 Lutter, F. H.; Grokenberger, L.; Hofmayer, M.; Knochel, P. manuscript in preparation

44

Poster 17Poster 19

The dual roles of Werner complexes in organic synthesis: chiral catalysts and in-situ chiral solvating agents

Quang H. Luu, John A. Gladysz* Department of Chemistry, Texas A&M University, College Station, Texas 77842, USA


Lipophilic salts of the cobalt(III) trication [Co((S,S)-NH2CH(Ph)CH(Ph)NH2)3]3+ (- and -13+) were found to be effectivecatalysts for a number of reactions involving C–C, C–N, and C–F bond formation.1 All of those transformations are accomplished in an enantioselective fashion. Moreover, these complexes constitute a new class of chiral solvating agents (CSA).2 When treated with Λ-13+ 2X–

BArf– (X = Cl/I) in an NMR sample, separate sets of signals were

observed for enantiomers of chiral molecules. The ee values obtained by NMR integration are in agreement with HPLC data. Thus, using these complexes as the catalysts allows for a quick access to the reaction outcomes. Mechanistic studies indicate that substrates and analytes bearing Lewis basic functional groups are activated through hydrogen bonding with 12 NH units of 13+. Stereoselectivity shows a strong dependence on the identity of the anion X– in the catalyst, suggesting the presence of an ion-pairing effect.

Diastereomers of the trication [Co((S,S)-NH2CHPhCHPhNH2)3]3+

1 Luu, Q. H.; Gladysz, J. A. manuscripts in preparation.2 Luu, Q. H.; Lewis, K. G.; Banerjee, A.; Bhuvanesh, N.; Gladysz, J. A. Chem. Sci.

2018, 9, 5087-5099.

NH2

Co

NH2

NH2

H2N

H2NH2N Ph

Ph

Ph

Ph

Ph

Ph

3+

�-13+�-13+� 3+� � 3+

H2N

Co

H2NNH2N

H2

NH2

H2N

Ph

Ph

Ph

Ph

Ph

Ph

45

Poster 18Poster 20

Investigating Rhodium Catalyzed C-H Borylation Mark M. Mantell, Melanie S. Sanford

Department of Chemistry, University of Michigan, Ann Arbor, MI, USA


The C–H bonds of methane are generally considered to be more chemically inert than those of other hydrocarbons. As such, the development of methods for the selective C–H functionalization of methane remains a fundamental as well as practical challenge in catalysis. This poster will describe our group’s development of catalysts for the C–H borylation of methane with pinacol diborane (B2Pin2). In particular, with a Cp*Rh-based catalyst (Cp* = pentamethylcyclopentadienyl), this reaction proceeds in cyclohexane solvent to produce a mixture of mono- and di-borylated methane (CH3Bpin and CH2BPin2, respectively) as well as borylated cyclohexane (CyBPin). We describe the impact of cyclopentadienyl ligand substitution on various catalyst performance metrics, including reaction rate as well as selectivity for mono-borylation versus di-borylation versus solvent borylation.

46

Poster 19Poster 21

Ni-Catalyzed Reductive Cross-Electrophile Coupling of Alkyl Amines with Aryl Bromides

Raul Martin-Montero, R. Yatham, R. Martin*Institute of Chemical Research of Catalonia (ICIQ), The Barcelona Institute of Science

and Technology, Av. Països Catalans 16, 43007 Tarragona, Spain. ICREA, Passeig

Lluïs Companys, 23, 08010 Barcelona, Spain


Prompted by the ubiquity of aliphatic amines in a myriad of molecules that display biological relevance,1 chemists have been challenged to design catalytic late-stage functionalization techniques by sp3 C–N cleavage. As part of our ongoing interest in cross-electrophile coupling reactions and the recent successful implementation of pyrylium salts in cross-coupling reactions with well-defined organometallic reagents,2,3 we present herein a methodology for forging C–C bonds via sp3 C–N cleavage of simple aliphatic amines with aryl halides. The protocol exhibits broad applicability with a diverse set of substitution patterns on both aryl and amine counterparts, even in the context of late-stage functionalization of advanced synthetic intermediates.

1 (a) Ruiz-Castillo, P.; Buchwald, S. L. Chem. Rev. 2016, 116, 12564. (b) McGrath, N.

A.; Brichacek, M.; Njardarson, J. T. J. Chem. Educ. 2010, 87, 1348. 2 Serrano. E.; Martin. R.; Angew. Chem. Int. Ed. 2016, 55, 11207-11211. Börjesson. M.;

Moragas. T.; Martin. R. J. Am. Chem. Soc. 2016, 138, 7504-7507. Sun. S-Z.; Martin. R.

Angew. Chem. Int. Ed. 2018, 57, 3622-3625. 3 Basch. C. H.; Liao. J.; Xu. J.; Piane. J. J.; Watson. M. P. J. Am. Chem. Soc. 2017. 139.

5313-5316.

BrR1 +

R3

R2NR1

R3

R2R2 Ni catalyst

Excellent yields&

broad scope

47

Poster 20Poster 22

New pincer-type PYA Ru(II) complexes: Facile modification towards powerful transfer hydrogenation catalysts

Philipp Melle, Martin Albrecht Departement für Chemie, Universität Bern, Freiestrasse 3, 3012 Bern, Switzerland


Ligand systems that offer flexibility and assist the metal in catalytic bond making and breaking have received much attention recently.1

Pyridylidene amide (PYA) ligands have been shown to be electronically flexible N-donor sites and have successfully been used for several applications in homogeneous catalysis, such as in challenging water oxidation and transfer hydrogenation.2 Here we will present new pincer-type ligands containing two PYA units. We will discuss the influence of different PYA ligand systems and the variation of spectator ligands on the electrochemical and photochemical properties of the Ru(II) complexes, as well as the evolution of catalytic performance of these PYA-pincer complexes to attractive transfer hydrogenation catalysts.

Tunable Ru(II) complexes containing pincer-type PYA ligands

1 Khusnutdinova J. R., Milstein D.; Angew. Chem. Int. Ed. 2015, 54, 12236-12273.2 Navarro M., Li M., Müller-Bunz H., Bernhard S., Albrecht M.; Chem. Eur. J., 2016, 22,

6740-6745.

48

Poster 21Poster 23

Chagosensine: Total Synthesis and Stereochemical Revision John J. Murphy, Marc Heinrich, Alois Fürstner

Max-Planck-Institut für Kohlenforschung, Kaiser-Wilhelm-Platz 1,

45470 Mülheim an der Ruhr, Germany


The unique architecture of the marine macrolide Chagosensine: a Z,Z-chlorodiene embedded in a highly oxidized and strained 16-memebred macrocycle, renders it an enticing synthetic target. Isolated in 2003 as a secondary metabolite of the sponge Leucetta chagosensis, the putative structure of this molecule was prepared by us in 2018 in 22 (LLS) steps.1 The synthetic methyl ester of chagosensine was found to have substantially different spectroscopic data than the natural sample, suggesting the original stereochemical assignment to be incorrect.2 In an effort to identify the correct stereoisomer of the macrolide, a northern fragment featuring a diastereomerically inverted tetrahydrofuran has been prepared in 14 steps using a modified synthetic sequence. Additionally, all four diastereomers of the diol unit in the southern fragment have been prepared in 14-15 steps using two novel routes.

Stereodivergent synthetic route for reassignment of Chagosensine

1 Heinrich, M.; Murphy, J. J.; Ilg, M. K.; Letort, A.; Flasz, J.; Philipps, P. Fürstner, A.,

Angew. Chem. Int. Ed., 2018, 57, 13575-13581. 2 Řezanka, T.; Hanuš, L.; Dembitsky, V. M., Eur. J. Org. Chem., 2003, 4073–4079.

49

Poster 22Poster 24

Asymmetric Formation of γ-Lactams via C−H Amidation Enabled by Chiral Hydrogen-Bond-Donor Catalysts

Yoonsu Parka,b, Sukbok Changa,b aDepartment of Chemistry, Korea Advanced Institute of Science and Technology

(KAIST) bCenter for Catalytic Hydrocarbon Functionalizations, Institute for Basic Science (IBS),

Daejeon 34141, Republic of Korea


Chiral γ-lactams are effective structural motifs found in numerous pharmaceutical agents. Here, we report iridium catalyst systems that overcome this challenging task by utilizing chiral hydrogen-bond-donor ligands.1 This protocol employs easily accessible carboxylic acid derivatives,2-4 which displayed an excellent efficiency and unprecedented enantioselectivity towards direct amidation of various types of sp3 C−H bonds. Computational investigations revealed an intramolecular hydrogen bonding as the key component for excellent enantioselectivity, and experimental evidences further corroborated active involvement of this non-covalent interaction during catalysis.

1 Park, Y.; Chang, S. Nat. Catal. 2019, accepted for publication. 2 Hong, S. Y.†; Park, Y.†; Hwang, Y.; Kim, Y. B.; Baik, M.-H.; Chang, S. Science 2018,

359, 1016. (†co-first authors) 3 Park, Y.; Heo, J.; Baik, M.-H.; Chang, S. J. Am. Chem. Soc. 2016, 138, 14020. 4 Park, Y.; Park, K. T.; Kim, J. G.; Chang S. J. Am. Chem. Soc. 2015, 137, 4534.

50

Poster 23Poster 25

Chemical valorization of renewable resources via (isomerizing)olefin-metathesis

Jacqueline Pollini, Lukas J. GooßenLehrstuhl für Organische Chemie I, Ruhr Universität Bochum, 44801 Bochum, Germany


Olefin-metathesis is a unique way of C–C bond formation, by cleaving and re-forming double bonds in an almost thermoneutral fashion. Isomerizing metathesis, where an isomerization catalyst continuously moves double bonds, while a metathesis catalyst scrambles the residues at the double bonds, has recently emerged as a valuable tool in organic chemistry.1 Through such processes the shortened intermediates of the components of the waste by-product cashew nutshell liquid (CNSL) can be transformed into their hydroxystilbene-analogues via a continuous shortening byisomerizing metathesis and a subsequent self-metathesis.2 On the other side the olefinic side-chain can be also elongated to form a biological active tyrosinase inhibitor via a cross-metathesis and a subsequent hydrogenation.3

anacardic acid cardol cardanol

CNSL

1.

2. H2

[Pd/Ru]

[Ru]

[Ru]7

7

Figure 1: Catalytic transformation of cashew nutshell liquid.

1 A. Behr, A. J. Vorholt, K. A. Ostrowski, T. Seidensticker, Green Chem. 2014, 16, 982.2 A. S. Trita, L. C. Over, J. Pollini, S. Baader, S. Riegsinger, M. a. R. Meier, L. J.

Gooßen, Green Chem. 2017, 19, 3051–3060.3 J. Pollini, V. Bragoni, L. J. Gooßen, Beilstein J. Org. Chem. 2018, 14, 2737–2744.

51

Poster 26

Palladium-Catalyzed Hydride Addition/C(sp2)–H Bond Activation Sequence

José F. Rodríguez, Ivan Franzoni, Katherine I. Burton, David A. Petrone, Ina Scheipers, Mark Lautens*

Davenport Research Laboratories, Department of Chemistry, University of Toronto, 80

St. George Street, Toronto, Ontario M5S 3H6, Canada


We present the use of ammonium halide salts as metal-hydride precursors in a Pd-catalyzed cycloisomerization of 1,6-diynes. This cascade process includes an overall anti-hydropalladation across an alkyne, intramolecular carbopalladation, and C(sp2)–H bond activationsequence, which affords silylated 2-azafluorenes. The synthetic utility of the products was demonstrated via a series of orthogonal derivatizations. Combined experimental and computational studies support an E-to-Z isomerization of a vinyl–Pd(II) intermediate, andsuggest two operative mechanisms depending on the concentration of the base in solution.

1 Petrone, D. A.; Franzoni, I.; Ye, J.; Rodríguez, J. F.; Poblador-Bahamonde, A. I.;

Lautens, M. J. Am. Chem. Soc. 2017, 139, 3546–3557.2 Rodríguez, J. F.; Burton, K. I.; Franzoni, I.; Petrone, D. A.; Scheipers, I.; Lautens, M.

Org. Lett. 2018, 20, 6915–6919.

N

OR1

[Si]

N

[Si]

R1O

R2

R2

Et3N•HI• practical• stable

+

Hcat. [Pd(PtBu3)2]cycloisomerization

N

PdIII[Si]

R1O

H

H R2

NR1O

H

[Si]

IPdIIR2

C(sp2)–H Activation

52

Poster 25Poster 27

Transition metal-catalyzed Dehydroperoxidation of Alkyl hydroperoxides

Elena Seminaa, Sara Sabatera, Jessica N. Hamanna, Marko Hermsena, Anna-Corina Schmidta, Joaquim H. Telesb, R. Paciellob, A.

Stephen K. Hashmia,c, Thomas Schauba,b

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

69120 Heidelberg, Germany. b BASF SE, Synthesis & Homogeneous Catalysis, Carl-

Bosch-Straße 38, 67056 Ludwigshafen, Germany. c Institute of Organic Chemistry,

Ruprecht-Karls-University Heidelberg, Im Neuenheimer Feld 270, 69120 Heidelberg,

Germany.


Nylon 6 is one of the most widely-used nylon which is produced via the ring-opening polymerization of ε-caprolactam at high temperatures. The starting material for the synthesis of ε-caprolactam is cyclohexanone that is formed from cyclohexane in an oxidation process (Scheme 1). In order to minimize the number of process steps in the production of εcaprolactam, a selective decomposition of the hydroperoxide solely to the ketone and one equivalent water would be an attractive target. Cr(VI) catalysts are known for the selective decomposition of cyclohexyl hydroperoxide. Homogenous and heterogeneous catalyst systems were investigated with respect to the favored formation of cyclohexanone. The focus was put on mechanistic studies using different spectroscopic methods.1

Scheme 1: Production of cyclohexanone.

1 Hamann J. N., Hermsen M., Schmidt A.C., Krieg S., Schießl J., Riedel D., Teles J.

H., Schäfer A., Comba P., Hashmi A. S. K., Schaub T. ChemCatChem, 2018,10, 2755.

53

Poster 26Poster 28

Selective Ruthenium-Catalyzed Transformation of Carbon Dioxide – an Alternative Approach towards Formaldehyde

Max Siebert, Oliver Trapp* Department Chemie, Ludwig-Maximilians-Universität München,

Butenandtstr. 5-13, 81377 München, Germany


Utilization of CO2 as a feedstock for the industrially important precursor formaldehyde is an opportunity to rebalance the carbon cycle and to reduce CO2 emissions, while providing an attractive alternative to the established energetically unfavorable and atom inefficient industrial synthesis of formaldehyde.[1] We present a highly selective one-step catalytic hydrogenation of carbon dioxide to a formaldehyde derivative using a homogeneous ruthenium catalyst. Here, formaldehyde is obtained as its dimethyl acetal, dimethoxymethane (DMM), at moderate temperatures (90°C) and partial pressures (90 bar H2 / 20 bar CO2) in the presence of methanol. The side product, methyl formate (MF) can be further transformed to dimethoxymethane in a consecutive catalytic step. Maximum turnover numbers of 786 for dimethoxymethane and 1290 for methyl formate were achieved with remarkable selectivities of over 90% for dimethoxymethane.[2]

1 Reuss, G.; Disteldorf, W.; Gamer, A.O.; Hilt, A. Formaldehyde, Ullmann´s

Encyclopedia of Industrial Chemistry, DOI: 10.1002/14356007.a11_619. 2 Siebert, M.; Seibicke, M., Siegle, A. F.; Kräh, S.; Trapp, O. J. Am. Chem. Soc. 2018,

DOI: 10.1021/jacs.8b10233.

54

Poster 27Poster 29

Enabling CO2 re-use for the production of cyclic carbonates Myriam Y. Souleymanoua, Cyril Godarda, Anna M. Masdeu-Bultóa,

Carmen Claverb

a Department of Physical and Inorganic Chemistry, University Rovira i Virgili,

Tarragona b Chemistry Technology Center of Catalonia, Tarragona, Spain


Carbon dioxide is a main greenhouse gas and a reduction of its emission is a global challenge. An active goal is to take this carbon-trapped in a waste product and re-use it to build useful chemicals [1]. In line of this, the synthesis of cyclic carbonates from CO2 is among the most promising processes for its chemical utilization. Such a use of CO2 as renewable one-carbon (C1) building block in organic synthesis contribute to a greener and more sustainable chemical industry.

In this contribution, a methodology based on the use of immobilized organocatalytic system for the cycloaddition of CO2 to epoxides is presented. By applying immobilization techniques, the features of the organocatalytic system are extended to the recyclability that offers heterogeneous catalysis.

1 Peters, M. Köhler, B. Kuckshinrichs, W. Leitner, W. Markewitz, P. Müller, T. E.

Chemsuschem 2011, 4, 1216. J. A. Rodriguez, P. Liu, D. J. Stacchiola, S. D.

Senanayake, M. G. White, J. G. Chen, ACS Catal. 2015, 5, 6696

OHOH

HO

O

OH

OHO

OR1

R2

OO

O

R1R2

1

O O

NN

R

RR

R

OO

Immobilized organocatalystonto rGo via pi-pi stacking interactions1

55

Poster 28Poster 30

Study of Precatalyst Degradation Leading to the Discovery of aNew Ru0 Precatalyst for Hydrogenation and Dehydrogenation

D. J. Tindalla, A. Anabya, M. Schelwiesb, J. Schwabenb, F. Romingerc,A. S. K. Hashmia,c, T. Schauba,b

a Catalysis Research Laboratory (CaRLa), Im Neuenheimer Feld 584, 69120

Heidelberg, Germany; b BASF SE, Synthesis and Homogeneous Catalysis, Carl-

Bosch-Straße 38, 67056 Ludwigshafen, Germany; c Organisch-Chemisches Institut,

Heidelberg University, Im Neuenheimer Feld 270, 69120 Heidelberg, Germany.


The complex Ru-MACHO (1) is a widely used precatalyst for hydrogenation and dehydrogenation reactions under basic conditions. The stoichiometric reaction of 1 with base in the absence of a substrate resulted in a fast degradation to a plethora of products of which three complexes were characterized in the solid state. One of the decomposition products, the Ru0 complex 2, was prepared independently and studied. The results of this study and the performance of 2 in hydrogenation and dehydrogenation reactions are presented.1

1 A. Anaby, M. Schelwies, J. Schwaben, F. Rominger, A. S. K. Hashmi, T. Schaub,

Organometallics 2018, 37, 2193−2201.

56

Poster 29Poster 31

Base Free Hydrogenation of Carbon Dioxide to Methyl Formate Using a Homogeneous Tripodal Ruthenium Catalyst

Niklas Westhues, Jürgen KlankermayerInstitut für Technische und Makromolekulare Chemie, RWTH Aachen University,

Worringerweg 2, 52074 Aachen, Germany


The chemical utilization of carbon dioxide (CO2) is a topic of enduringinterest and great current dynamic. Especially the selective reduction of CO2 with the assistance of bases has been investigated in great detail and effective catalysts for the synthesis of formic acid and its base adducts could be developed.[1] However, only a few homogeneous catalytic systems enable the important base freeconversion of CO2 to methyl formates with moderate activity and selectivity.[2]

Herein, a highly active and selective catalytic system based on a tailored molecular homogenous tripodal ruthenium catalyst is described, facilitating the transformation of CO2 to methyl formate withhigh TONs at low temperatures.

Scheme 1: Base free homogeneous catalyzed hydrogenation of CO2

to methyl formate.

1 a) W. Wang, S. Wang, X. Ma, J. Gong, Chem. Soc. Rev. 2011, 40, 3703-3727; b) J.

Klankermayer, S. Wesselbaum, K. Beydoun, W. Leitner, Angew. Chem. Int. Ed. 2016,

55, 7296-7343.2 a) K. Thenert, K. Beydoun, J. Wiesenthal, W. Leitner, J. Klankermayer, Angew. Chem.

Int. Ed. 2016, 55, 12266-12269; b) C. A. Huff, M. S. Sanford, J. Am. Chem. Soc. 2011,

133, 18122-18125.

57

Poster 32

Grafting of a molecular rhenium CO2 reduction catalyst onto colloidal imprinted carbon

Janina Willkomm, Erwan Bertin, Marwa Atwa, Viola Birss, Warren E.Piers

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

AB, T2N 1N4, Canada


The electrochemical conversion of CO2 is considered a viable route to sustainably produce fuels or chemical feedstocks, such as methanol or CO.1 [Re(2,2’-bipyridine)(CO)3Cl] and its derivatives are a well-explored type of molecular catalysts operating with high efficiency andselectivity for CO2-to-CO reduction.2 Recent advances in this field include their integration with solid-state materials to assemble CO2-reducing electrodes.3 In this work, an aminophenethyl-substitued Re complex was tethered to mesoporous colloidal imprinted carbon (CIC) via an oxidative grafting method, and the hybrid electrode tested for its stability and activity under catalytic conditions.

Schematic representation of the CIC|Re hybrid electrode

1 Kondratenko, E. V.; Mul, G.; Baltrusaitis, J.; Larrazábal, G. O.; Pérez-Ramírez, J.,

Energy Environ. Sci. 2013, 6, 3112-3135.2 Clark, M. L.; Cheung, P. L.; Lessio, M.; Carter, E. A.; Kubiak, C. P., ACS Catal. 2018,

8, 2021-2029.3 Zhanaidarova, A.; Ostericher, A. L.; Miller, C. J.; Jones, S. C.; Kubiak, C. P.,

Organometallics 2018, DOI: 10.1021/acs.organomet.8b00547.

58

Poster 31Poster 33

New transmetalation reagents for the gold-catalyzed photochemistry

Sina Witzela, Jin Xieb, A. Stephen K. HashmiaaInstitute of Organic Chemistry, Heidelberg University, Im Neuenheimer Feld 270,

69120 Heidelberg, GermanybSchool of Chemistry and Chemical Engineering, Nanjing University, Hankou Road 22,

210093 Nanjing, China


The chemistry of UV and visible light-mediated photoredox gold(I/III)catalysis has received great interest in the last years and already versatile methods towards highly applicable scaffolds were developed. We have focused our efforts on designing alternative photo-inducedmethodologies only mediated by a gold catalyst and thus expanding the applicability by exploring new transmetalation reagents.1-5

1 Huang, L.; Rudolph, M.; Rominger, F.; Hashmi, A. S. K. Angew. Chem. Int. Ed. 2016,

55, 4808-4813. 2 Huang, L.; Rominger, F.; Rudolph, M.; Hashmi, A. S. K. Chem.

Commun. 2016, 52, 6435-6438. 3 Witzel, S.; Xie, J.; Rudolph, M.; Hashmi, A. S. K, Adv.

Synth. Catal. 2017, 359, 1522-1528. 4 Xie, J.; Sekine, K.; Witzel, S.; Krämer, P.;

Rudolph, M.; Hashmi, A. S. K. Angew. Chem. Int. Ed. 2018, 57, 16648-16653. 5 Witzel,

S.; Sekine, K.; Rudolph, M.; Hashmi, A. S. K. Chem. Commun. 2018, 54, 13802-13804.

59

Poster 32Poster 34

Cobalt-catalyzed Asymmetric Hydrogenation in Protic Solvents Aaron Zhong

Department of Chemistry, Princeton University, Princeton, New Jersey 08544,

United States


Transition metal-catalyzed asymmetric hydrogenation has found widespread application in pharmaceutical, flavor and fragrance, agrochemical and fine chemical industries. Development of catalysts based on first-row transition metals as alternatives to the widely used precious metals are attractive due to cost, sustainability as well as new reactivity, selectivity and mechanism of operation. Here I present our recent discovery on cobalt-catalyzed asymmetric hydrogenation of enamides and unsaturated carboxylic acids. Using high-throughput methods, optimal ligand(Ph-BPE), cobalt source(CoCl2) and activator(zinc dust) were identified and the epilepsy medication, levetiracetam, could be produced via asymmetric hydrogenation on a 200 gram scale with 0.08 mol% catalyst loading1. The cobalt catalyst operates optimally in methanol, a solvent that’s usually deleterious for low-valent first-row metals. A variety of chiral acids can also be produced using this method, including Naproxen, Flurbiprofen and a L-DOPA precursor.

1 Friedfeld, M. R.; Zhong, H.; Ruck, R. T.; Shevlin, M.; Chirik, P. J. Science, 2018, 360,

888-8932 Zhong, H.; Friedfeld, M. R.; Camacho-Bunquin, J.; Sohn, H.; Yang, C.; Delferro, M.;

Chirik, P. J. Organometallics, 2018, asap

0.084 mol% (R,R)-Ph-BPE0.08 mol% CoCl2•6H2O

0.8 mol% Zn dust

N

NH2

O

O N

NH2

O

OMeOH, 50 °C, 16 h500 psi H2

P

P

Ph

Ph

Ph

Ph

(R,R)-Ph-BPElevetiracetam (Keppra®)

97.0% isolated yield, 98.2% ee

60

Poster 33Poster 35

Enantioselective Allylation Using Allene, a Petroleum Cracking By-product1

Yujing Zhou, Richard Y. Liu, Yang Yang, Stephen L. Buchwald Department of Chemistry, Massachusetts Institute of Technology, USA


Allene (C3H4) gas is produced and separated on million-metric-ton scale per year during petroleum refining but is rarely employed in organic synthesis. Meanwhile, the addition of an allyl group (C3H5) to ketones is among the most common and prototypical reactions in synthetic chemistry. Herein, we report that the combination of allene gas with inexpensive and environmentally benign hydrosilanes, such as PMHS, can serve as a replacement for stoichiometric quantities of allylmetal reagents, which are required in most enantioselective ketone allylation reactions. This process is catalyzed by copper catalyst and commercially available ligands, operates without specialized equipment or pressurization, and tolerates a broad range of functional groups. Furthermore, the exceptional chemoselectivity of this catalyst system enables industrially relevant C3 hydrocarbon mixtures of allene with methylacetylene and propylene to be applied directly.

CuH-Catalyzed Enantioselective Allylation of Ketones Using Allene

1 Liu, R. Y.†; Zhou, Y.†; Yang, Y.; Buchwald, S. L. submitted

61

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1112th CaRLa Winter School 2018 Winter School 2019 Heidelberg€¦ · Flash Poster Presentation (FPP) FPP FPP, BASF Career- Lunch Poster Prize Ceremony & Closing Remarks 12:00 –