6th carla winter school 2013...

6th CaRLa Winter School

2013 Heidelberg

February 23 – March 1, 2013

Final Program

Welcome to the 6th CaRLa Winter School

Welcome to the picturesque town of Heidelberg, welcome to CaRLa, the joint research laboratory of BASF and University of Heidelberg and welcome to our CaRLa Winter School on Homogeneous Catalysis!

With our Winter School, we aim to foster intense scientific exchange between established and young researchers in the field of homogeneous catalysis.

The conference takes place from February 23 – March 1, 2013 at the German-American-Institute downtown Heidelberg, within walking distance to the old town.

Our scientific program consists of 1 Keynote Lecture, 10 lectures, 10 problem set sessions, 4 poster sessions and 8 sessions with flash poster presentations.

The days are organized as a morning and afternoon session. Each session is divided into two parts; the first part consists of a scientific lecture while the second part has a more educational focus. Between the two sessions of the day, we have scheduled a prolonged lunch break for individual use. In the evening, we have planned short poster presentations of selected poster contributions, after which a light dinner is served in parallel with the poster sessions.

All presentations are scheduled to leave enough room for discussion and we encourage every participant to use this time to make our Winter School an exciting event for science.

The conference is fully sponsored by BASF and we are happy to announce, that we will have the opportunity for making an excursion to BASF on Thursday afternoon.

We hope that all participants will have a pleasant and scientifically stimulating stay in Heidelberg during our Winter School.

If we can assist you in any way to make your stay in Heidelberg more pleasant, please do not hesitate to contact us.

Michael Limbach Peter Hofmann

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Saturday, 23rd February until 16:00 Arrival and Coffee Break 16:30 Welcome Address Thomas Rausch

Prorector of Ruprecht-Karls-University, Heidelberg

17:00 Key Note Lecture Friedhelm Balkenhohl, BASF SE

“Raw Material Change in the Chemical Industry”

18:00 Light Dinner and “Get-together”

Sunday, 24th February 9:00 Lecture: Frustrated Lewis Pairs – Principle and Some Recent Developments

(Gerhard Erker)

10:00 Coffee Break

10:15 Training Session: 1,1-Carboboration Reactions - New Tools and New

Applications

(Gerhard Erker)

11:15 Coffee Break

11:30 Flash Poster Presentations: Posters 2, 4, 6, 8, 10

12:00 Free Time (Lunch)

14:30 Lecture: Dehydrogenation and tandem-catalyzed reactions of alkanes

(Alan S. Goldman)

15:30 Coffee Break

3

15:45 Training Session: Breaking and making C(sp3)-F and C(sp3)-O bonds with

pincer-ligated iridium complexes. A case study in mechanistic investigation and

catalyst design

(Alan S. Goldman)

16:45 Coffee Break


17:30 Poster Session including light dinner

Monday, 25th February

9:00 Lecture: A New Class of Catalysts for Enantioselective Organic Reactions: Metal-

Containing Chiral Hydrogen Bond Donors

(John Gladysz)

10:00 Coffee Break

10:15 Training Session: The Publication Process from the Perspective of an Editor-in-

Chief of an American Chemical Society Journal (Organometallics)

(John Gladysz)

11:15 Coffee Break



14:30 Lecture: Enantioselective Catalysis with New Chiral Pincer Ligands

(Lutz H. Gade)

4

15:30 Coffee Break

15:45 Training Session: Symmetry as Construction Principle in Asymmetric Catalysis

(Lutz H. Gade)

16:45 Coffee Break



Tuesday, 26th February

9:00 Lecture: Applied Organometallic Chemistry - Menthol Synthesis

(Rocco Paciello)

10:00 Coffee Break

10:15 Training Session: Applied Organometallic Chemistry - CO2-Hydrogenation

(Rocco Paciello)

11:15 Coffee Break



14:30 Lecture: Asymmetric Pd-NHC* Catalyzed Coupling Reactions

(Hans-Peter Kündig)

15:30 Coffee Break

5

15:45 Training Session: Aspects of Planar Chiral Transition Metal Complexes

(Hans-Peter Kündig)

16:45 Coffee Break



Wednesday, 27th February

9:00 Lecture: Cobalt-Mediated Oxidations: Electrocatalytic Water Splitting and

Hydrocarbon Activations with High Valent Molecular Systems

(T. Don Tilley)

10:00 Coffee Break

10:15 Training Session: Unusual Transformations for Metal-Silicon-Hydrogen

Complexes: Electronic Structures and Electron Bookkeeping in "Hydride" Species

(T. Don Tilley)

11:15 Coffee Break



14:30 Lecture: Base-Assisted C-H Bond Functionalizations

(Lutz Ackermann)

15:30 Coffee Break

6

15:45 Training Session: Applications of C-H Bond Functionalization to Organic

Synthesis

(Lutz Ackermann)

16:45 Coffee Break



Thursday, 28th February 9:00 Lecture: Cooperative Metal Amide Interactions: From Dehydrogenations,

Organometallic Fuel Cells, and Methanol Conversion

(Hansjörg Grützmacher)

10:00 Coffee Break

10:15 Training Session: Metal Ligand Cooperation

(Hansjörg Grützmacher)


13:00 Transfer to Ludwigshafen

13:30 Excursion of BASF’s Main Site in Ludwigshafen

18:00 Winter School Dinner in “Kulturbrauerei”

7

Friday, 1st March 9:00 Lecture: Reactions of Late Transition Metal Alkyl and Hydride Complexes with

Molecular Oxygen

(Karen I. Goldberg)

10:00 Coffee Break

10:15 Training Session: Brainstorming New Project Ideas (Karen I. Goldberg)

11:15 Coffee Break

11:30 Poster Prize Ceremony & Closing Remarks

12:00 Departure

8

Lectures & Training Sessions

9

Raw Material Change in the Chemical Industry Friedhelm Balkenhohl*

BASF SE, Synthesis and Homogeneous Catalysis, GCS – M313, 67056 Ludwigshafen, Germany

e-mail: [email protected]

At each time availability and price structure of the fossil raw materials coal,

petroleum and natural gas have significantly influenced the technological basis and consequently the buildup and development of the chemical industry. In the energy industry a consistent raw material change from coal to oil and gas has occurred since the middle of the 20th Century. The reason for this change lies mainly in the simpler logistics as well as the versatile usefulness of oil and gas. Parallel to the change in the energy industry the raw material base of the chemical industry has been changed from coal to oil and gas. Olefins, which are produced mainly by steam cracking of naphtha, and aromatic hydrocarbons, are still the crucial raw materials for the majority of the value added chains of the chemical industry. Price volatility, regional distribution and the finite reserves of crude oil are the main drivers for the development of conversion technologies to utilize alternative raw materials, e.g. natural gas, coal, renewables and carbon dioxide as feedstocks for the chemical industry.

10

Frustrated Lewis Pairs - Principle and Some Recent Developments

Gerhard Erker*

Organisch-Chemisches Institut der Universität Münster, Germany


Frustrated Lewis pair (FLP) chemistry has taken an exciting development in the

recent years. FLPs are comprised of Lewis acids and Lewis bases that have become

hindered from the ubiquitous neutralizing adduct formation either by steric bulk or by

electronic means. The situation of co-existent active Lewis acid/base pairs in solution

creates a situation where new reactions can be found by cooperative or synergistic

action with added substrates. FLP chemistry has been used for the metal-free activation

of a variety of small molecules. In this lecture some recent results in FLP chemistry are

presented, focussing especially on the reactions of intramolecular FLPs. We will discuss

dihydrogen activation by such systems and the development of metal-free

hydrogenation catalysts. A variety of other FLP reactions will be presented, including

carbon dioxide and carbon monoxide chemistry and the FLP chemistry with nitrogen

monoxide. We will see how FLP chemistry can contribute to the synthesis of novel

unsaturated phosphorus and boron compounds and explore some of their unique

chemistry.

Selected references:

"Frustrated Lewis-pairs: Metal-free Hydrogen Activation and More", D. W. Stephan, G. Erker, Angew.

Chem. Int. Ed. 2010, 49, 46-76-

"Reaction of Frustrated Lewis Pairs with Conjugated Ynones Selective Hydrogenation of the Carbon-

Carbon Triple Bond", B.-H. Xu, G. Kehr, R. Fröhlich, B. Wibbeling, B. Schirmer, S. Grimme, G Erker,

Angew. Chem. Int. Ed. 2011, 50, 7183-7186.

"N,N-Addition of Frustrated Lewis Pairs to Nitric Oxide: An Easy Entry to a Unique Family of Aminoxyl

Radicals", M. Sajid, A. Stute, A. J. P. Cardenas, B. J. Culotta, J. A. M. Hepperle, T. H. Warren, B.

Schirmer, S. Grimme, A. Studer, C. G. Daniliuc, R. Fröhlich, J. L. Petersen, G. Kehr, G Erker, J. Am.

Chem. Soc. 2012, 134, 10156-10168.

"Frustrated Lewis pairs: Some recent developments", G. Erker, Pure Appl. Chem. 2012, 84, 2203-2217.

11

1,1-Carboboration Reactions - New Tools and New Applications

Gerhard Erker*

Organisch-Chemisches Institut der Universität Münster, Germany


Vinylboranes are important reagents for organic synthesis. They have increasingly

become important boron Lewis acids useful for catalytic and stoichiometric applications.

One of the best way of making substituted vinylboranes is by the 1,1-carboboration

reaction. The early development of this reaction type is to a large extent due to the work

by Professor Bernd Wrackmeyer (“Wrackmeyer reaction”). Recently we and a few

others have developed advanced versions of the 1,1-carboboration reaction making use

of the strongly electrophilic R-B(C6F5)2 type borane reagents. These can be used for

converting a variety of simple organic alkynes into the respective alkenyl boranes under

very mild reaction conditions. In this tutorial a variety of recent examples are discussed

in some detail, including an evaluation of the respective NMR spectra of selected

examples. This includes organometallic variants and the advanced syntheses of

substituted phospholes and other important heterocyclic systems.

Selected references: "1,1-Carboboration", G. Kehr, G. Erker, Chem. Commun. 2012, 48, 1839-1850.

"The 1,1-Carboboration of Bis(alkynyl)phosphanes as a Route to Phosphole Compounds", J. Möbus, Q.

Bonnin, K. Ueda, R. Fröhlich, K. Itami, G. Kehr, G. Erker, Angew. Chem. Int. Ed. 2012, 51, 1954-1957.

"Preparation of Dihydroborole Derivatives by a Simple 1,1-Carboboration Route", A. Feldmann, A. Iida,

R. Fröhlich, S. Yamaguchi, G. Kehr, G. Erker, Organometallics 2012, 31, 2445-2451.

"1,1-Carboboration Route to Substituted Naphthalenes", R. Liedtke, M. Harhausen, R. Fröhlich, G. Kehr,

G. Erker, Org. Lett. 2012, 14, 1448-1451.

12

Dehydrogenation and tandem-catalyzed reactions of alkanes

Alan S. Goldman*

Rutgers, the State University of New Jersey, Department of Chemistry & Chemical Biology,

Wright-Rieman Laboratories, Office 180, 610 Taylor Road, Piscataway, NJ 08854, USA


Pincer-ligated iridium complexes have proven to be highly effective

catalysts for the dehydrogenation of alkanes. In addition to simple

dehydrogenation, we have exploited these systems for the catalytic

metathesis of alkanes, dehydroaromatization, and other tandem-catalytic

reactions. The development and the mechanistic and theoretical study of

these catalysts will be described. The factors governing the thermodynamics

and kinetics of the individual reaction steps have been investigated, with

emphasis on the oxidative addition of carbon-hydrogen and other covalent

bonds. The question of regioselectivity in both alkane dehydrogenation and

the addition of alkane C-H bonds will be addressed.

13

Breaking and making C(sp3)-F and C(sp

3)-O bonds with pincer-ligated

iridium complexes. A case study in mechanistic investigation and

catalyst design

Alan S. Goldman*

Rutgers, the State University of New Jersey, Department of Chemistry & Chemical Biology,

Wright-Rieman Laboratories, Office 180, 610 Taylor Road, Piscataway, NJ 08854, USA


An investigation of potential routes to C-H bond functionalization by

pincer-ligated iridium complexes has led us from C-H bond addition, to C-C

bond formation, to C-O and C-F bond cleavage, back to C-H bond addition

and then to C-O bond formation(!). Mechanistic study, and DFT calculations

have been essential to the progress in this work. Isotope effect experiments

and competition experiments more generally have played a critical role.

Fundamental questions concerning such experiments and their relationship

to catalyst design will be discussed.

14

A New Class of Catalysts for Enantioselective Organic Reactions: Metal-Containing Chiral Hydrogen Bond Donors

John A. Gladysz*

Department of Chemistry, Texas A&M University, PO Box 30012, College Station, Texas 77842-3012,

USA


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

3+, and related species, have played important historical roles in the development of inorganic chemistry and stereochemistry.1,2 As Werner described in 1912, the two

enantiomers, commonly designated Λ and ∆, can be separated by crystallization of the diastereomeric tartrate salts.2b However, despite the low cost and ready availability of the building blocks, there have been no applications in enantioselective organic synthesis.

We have found that [Co(en)3]3+ and related cations can be rendered soluble in organic

solvents by using lipophilic anions such as "BArf–".3 Suitably functionalized derivatives

act as highly enantioselective catalysts for a variety of carbon-carbon bond forming reactions. The mechanisms involve outer sphere activation of the electrophile by hydrogen bonding to the NH moieties. Other types of metal-containing chiral hydrogen bond donors are also effective, including a chelate of the CpRuL fragment.

[1] Kauffman, G. B. Coord. Chem. Rev. 1974, 12, 105-149.

[2] For the first enantiopure cobalt complex, see Werner, A. Chem. Ber. 1911, 44, 1887-1898; For

the first enantiopure [Co(en)3]3+ species, see Werner, A. Chem. Ber. 1912, 45, 121-130.

[3] Ganzmann, C.; Gladysz, J. A. Chem. Eur. J. 2008, 14, 5397-5400.

15

The Publication Process from the Perspective of an Editor-in-Chief of an American Chemical Society Journal (Organometallics)

John A. Gladysz*

Department of Chemistry, Texas A&M University, PO Box 30012, College Station, Texas 77842-3012,

USA


Aspects of the publication process often seem arcane to graduate students, and

indeed there are many behind the scenes considerations apart from the ubiquitous author guidelines.1,2 The goal of this presentation will be to demystify the submission-to-publication process, with special attention to the stumbling blocks that the individual researchers and research supervisors often encounter. A sample manuscript may be presented and critiqued, and helpful handouts distributed. Case histories involving problem manuscripts may be described. Some ethical issues and new plagiarism catching software will also be discussed.

[1] http://pubs.acs.org/paragonplus/submission/orgnd7/orgnd7_authguide.pdf

[2] http://pubs.acs.org/styleguide

16

Enantioselective Catalysis with New Chiral Pincer Ligands Lutz H. Gade*

Anorganisch-Chemisches Institut, Universität Heidelberg, Im Neuenheimer Feld 270,

69120 Heidelberg, Germany


Meridionally coordinating chiral tridentate ligands, frequently referred to as

“pincers”,1 provide the structural platform for the construction of efficient stereodirecting molecular environments. Whilst many of the known chiral systems of the “pincer” type perform relatively poorly in enantioselective catalysis due to certain lack of control of substrate orientation, the assembly from rigid heterocyclic units recently has given rise to several highly enantioselective catalysts.2

We have recently developed a series of chiral stereodirecting pincer ligands which were found to be very efficient for a range of enantioselective transformations.3,4 Several case histories will be presented in the lecture as well as new aspects of catalyst characterization.5

[1] Reviews covering “pincer” complex chemistry: M. Albrecht, G. van Koten, Angew. Chem., Int.

Ed. 2001, 40, 3750-3781; M. van der Boom, D. Milstein, Chem. Rev. 2003, 103, 1759-1792.

[2] New Frontiers in Asymmetric Catalysis, (Eds.: K. Mikami, M. Lautens), Wiley: Hoboken, NJ,

2007; Catalysis in Asymmetric Synthesis, 2nd ed. (Eds.: V. Caprio, J. M. J. Williams), Wiley:

Hoboken, NJ, 2009; Catalytic Asymmetric Synthesis, 3rd ed. (Ed.: I. Ojima), Wiley: Hoboken,

NJ, 2010.

[3] B. K. Langlotz, H. Wadepohl, L. H. Gade, Angew. Chem. Int. Ed. 2008, 47, 4670-4674; D. C.

Sauer, H. Wadepohl, L. H. Gade, Inorg. Chem. 2012, 51, 12948-12958.

[4] Q.-H. Deng, H. Wadepohl, L. H. Gade, Chem. Eur. J. 2011, 17, 14922-14928; Q.-H. Deng, H.

Wadepohl, L. H. Gade, J. Am. Chem. Soc. 2012, 134, 2946-2949; Q.-H. Deng, H. Wadepohl,

L. H. Gade, J. Am. Chem. Soc. 2012, 134, 10769-10772.

[5] M. Kruck, H. Wadepohl, M. Enders, L. H. Gade, Chem. Eur. J. 2013, 19, 1599-1606.

17

Symmetry as Construction Principle in Asymmetric Catalysis Lutz H. Gade*

Anorganisch-Chemisches Institut, Universität Heidelberg, Im Neuenheimer Feld 270, 69120 Heidelberg,

Germany


Rotational symmetry of chiral catalysts may simplify catalyst development. It leads

to a reduction in the number of diastereomeric intermediates and transition states which constitute the complex reaction network underlying a catalytic process. This was first realized by Kagan three decades ago1 and has since been extensively exploited.2 This tutorial will focus on the development of stereodirecting ligands possessing C2- and C3-symmetry and the ways in which this leads to simpler stereochemistry and efficient catalysts.3

[1] H. B. Kagan, T. P. Dang, J. Am. Chem. Soc. 1972, 94, 6429.

[2] Early reviews: J. K. Whitesell, Chem. Rev. 1989, 89, 1581; H. Brunner, Top. Stereochem.

1988, 18, 129.

[2] See for example: C. Foltz, B. Stecker, G. Marconi, S. Bellemin-Laponnaz, H. Wadepohl, L. H.

Gade, Chem. Eur. J. 2007, 13, 9912; L. H. Gade, S. Bellemin-Laponnaz, Chem. Eur. J. 2008,

14, 4242.

18

Applied Organometallic Chemistry Part 1: Menthol Synthesis, Part 2: CO2-Hydrogenation

Rocco Paciello* Senior Research Manager, BASF SE, Synthesis and Homogeneous Catalysis Department

GCS/H – M313, 67056 Ludwigshafen Germany

e-mail: rocco.paciello @basf.com

Homogeneous catalysis research at BASF is characterized by a focus on

organometallic chemistry closely coupled with process engineering. The strength of this approach will be demonstrated using selected examples.

An efficient 3-step route to L-menthol starting from citral is presently being realized.

A continuous asymmetric hydrogenation was developed for the first step. The key

observations in process development can be correlated with the behavior of the catalyst system at a molecular level.

A process for hydrogenating CO2 to formic acid is also being developed. A new process concept combines an efficient recycling of the active ruthenium catalyst with the isolation of formic acid. This is achieved using a carefully matched combination of solvent, amine base and lipophilic catalyst and by exploiting the properties and phase behaviour of these components.

19

Asymmetric Pd-NHC* Catalyzed Coupling Reactions E. Peter Kündig*

Department of Organic Chemistry, University of Geneva, Geneva, Switzerland


The lecture will focus on the design of chiral monodentate N-heterocyclic carbene

ligands that enable high asymmetric inductions in the title reactions. Target molecules are 3,3-disubstituted oxindoles, aza-oxindoles and substituted indolines. The first two are prepared via intramolecular arylation of amides while the latter meet the challenge of CAr/Csp3-H coupling reactions.1,2 Functionalization of unactivated CAr-H bonds by metal catalyzed processes has emerged in recent years as a powerful tool in synthesis. Activation of Csp3-H bonds is gaining ground but asymmetric reactions involving an unactivated methylene group are extremely scarce. It is/was an interesting challenge. Most recent discoveries are regiodivergent reactions with cases where a racemic mixture is transformed into two equal parts of two structurally different indoline products of very high enantiomeric purity.

[1] Jia, Y.-X.; Katayev, D.; Seidel, T. M.; Bernardinelli, G.; Kündig, E. P. Chem. Eur. J. 2010, 16,

6300 and ref.cit.

[2] Katayev, D.; Nakanishi, M.; Bürgi, T.; Kündig, E.P. Chem. Sci. 2012, 3, 1422 and ref. cit.

20

Aspects of Planar Chital Transition Metal Complexes E. Peter Kündig*

Department of Organic Chemistry, University of Geneva, Geneva, Switzerland


We will discuss interactively the title topic touching on elements of stereochemical

nomenclature, resolution of racemates, diastereoselective - and enantioselective - syntheses using stoichiometric and catalytic transformations, examples of chiral ligands based on planar chirality and of their use as chirons in organic synthesis.1

[1] Eliel, E. L.; Wilen, S. H., Mander, L. N. Stereochemistry of Organic Compounds, Wiley: New

York; Muniz, K “Planar Chiral Arene Chromium Complexes as Ligands for Asymmetric

Catalysis” in “Topics in Organometallic Chemistry”, Kündig, E. P., Ed.; Springer-Verlag,

Heidelberg, 2004; Vol. 7, pp. 205-2024; Ogasawara, M.; Watanabe, S. Synthesis 2009,

1761-1785. Addendum. 2009, 3177-3178; Chiral Ferrocenes in Aymmetric Catalysis:

Synthesis and Applications, Dai, L. X.; Hou, X. L., Eds.; VCH: Weinheim, 2010.

21

Cobalt-Mediated Oxidations: Electrocatalytic Water Splitting and Hydrocarbon Activations with High Valent Molecular Systems

Kevin Ahn,a,b Tim Davenport,a,b Andy Nguyen,a,b T. Don Tilleya,b*

aDepartment of Chemistry, University of California, Berkeley, Berkeley, California 94563, USA; bChemical Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, California 94563, USA


The integration of photovoltaics and catalysts into a useful system for solar energy

conversion will require a number of advances, such as development of high efficiency, nanoscaled photovoltaic units, the discovery of inexpensive electrocatalysts for the half-reactions of interest, and the incorporation of efficient catalysts onto the surfaces of the photovoltaics. For schemes based on water oxidation, it is possible to envision catalysts derived from molecular transition metal complexes, or from inorganic solid-state materials. This presentation will describe molecular precursor methods for the generation of cobalt-based, nanostructured heterogeneous catalysts for water oxidation. These catalysts are thought to proceed via high-valent cobalt(IV) oxo species, which are also proposed intermediates in a number of catalytic, hydrocarbon oxidations utilizing cobalt. Thus, attempts have been made to synthesize oxo complexes of this type, and probe their chemistry. These studies have led to insights into the reactivity of high valent cobalt species, and to new C-H activations.

22

Unusual Transformations for Metal-Silicon-Hydrogen Complexes: Electronic Structures and Electron Bookkeeping in "Hydride" Species

T. Don Tilley*

Department of Chemistry, University of California, Berkeley, Berkeley, California 94563, USA


Transition-metal hydride complexes play important and pervasive roles in catalysis.

This is certainly the case in catalytic reactions that produce organosilicon compounds and polymers, which have numerous applications in modern society. Thus, new catalytic transformations are highly desired, and there is considerable interest in development of more cost-effective and selective hydrosilylation catalysts. A general approach to addressing these issues involves discovery of new fundamental reaction steps for activations of appropriate substrates. Invariably, catalytic reactions of organosilicon species involve key intermediates that possess both hydrogen and silicon within the coordination sphere of the metal. Transition metal–silicon–hydrogen complexes possess a wide array of structures that feature delocalized bonding over metal, silicon and hydrogen centers. Some of the more interesting structures of this type, involving bridging hydrogen atoms, can be difficult to describe with the simplest bonding models routinely employed by chemists.

This presentation and discussion will center on analyses of mechanisms and bonding descriptions for unusual metal-silicon complexes that mediate new mechanisms for transformations of organosilanes. Such complexes include unsaturated metal silylene complexes, sigma-complexes, and coordinatively unsaturated, first-row transition metal species. Discussion will center on use of simple bonding models for these complexes, with an emphasis on bridging hydrides.

23

Carboxylate-Assisted Metal-Catalyzed C–H Bond Functionalizations Lutz Ackermann*

Institute for Organic and Biomolecular Chemistry, Georg-August-University Göttingen,

Germany


Direct C–H bond functionalizations of (hetero)arenes are highly

attractive tools for an overall streamlining of synthetic chemistry, since these methods avoid the preparation of prefunctionalized starting materials.1 Recently, we introduced carboxylates as efficient cocatalysts for site-selective direct arylations and alkylations employing inexpensive ruthenium complexes.2,3 Detailed mechanistic insight into the C–H bond ruthenation step also set the stage for ruthenium-catalyzed twofold C–H bond functionalizations, as well as step-economical oxidative annulations of alkynes,4 which provide viable in an aerobic fashion with ambient air as the ideal oxidant.5

[1] Ackermann, L.; Vicente, R.; Kapdi, A. Angew. Chem. Int. Ed. 2009, 48, 9792;

Ackermann, L. Modern Arylation Methods, Wiley-VCH, Weinheim, 2009.

[2] Ackermann, L.; Novák, P.; Vicente, R.; Hofmann, N. Angew. Chem. Int. Ed.

2009, 48, 6045; Ackermann, L.; Vicente, R.; Althammer, A. Org. Lett. 2008, 10,

2299. (c) Ackermann, L. Chem. Rev. 2011, 111, 1315.

[3] Palladium-catalyzed transformations: Ackermann, L.; Althammer, A.; Fenner, S.

Angew. Chem. Int. Ed. 2009, 48, 201; Ackermann, L.; Althammer, A. Angew.

Chem. Int. Ed. 2007, 46, 1627.

[4] Ackermann, L.; Lygin, A. V.; Hofmann, N. Angew. Chem. Int. Ed. 2011, 50,

6503; Kozhushkov, S. I.; Ackermann, L. Chem. Sci. 2013,

DOI:10.1039/C2SC21524A.

[5] Ackermann, L.; Wang, L.; Lygin, A. V. Chem. Sci. 2012, 3, 177.

24

Applications of C–H Bond Functionalization to Organic Synthesis Lutz Ackermann*

Institute for Organic and Biomolecular Chemistry, Georg-August-University Göttingen, Germany


Recent applications of C–H bond functionalizations in organic synthesis will be

highlighted, with a particular focus on the preparation of

bioactive heterocycles and natural product synthesis.

Moreover, the mechanisms of the

key metal-catalyzed

direct functionalization

reactions will be discussed.1

[1] Ackermann, L. Chem. Rev. 2011, 111, 1315; Ackermann, L.; Vicente, R.; Kapdi, A. Angew.

Chem. Int. Ed. 2009, 48, 9792; Ackermann, L. Modern Arylation Methods, Wiley-VCH,

Weinheim, 2009.

25

Cooperative Metal Amide Interactions: From Dehydrogenations, Organometallic Fuel Cells, and Methanol Conversion

Hansjörg Grützmachera,b* aETH, Zürich, Switzerland; bSYSU Lehn Institute of Functional Materials, China


The development of an efficient catalytic process that mimics the enzymatic function

of alcohol dehydrogenase is critical for using biomass alcohols for the production of H2 as chemical energy carrier and fine chemicals under waste-free conditions. Our own research efforts focus on dehydrogenative coupling reactions (DHC) which is an atom economic and efficient way to obtain carbonic acids, ester, and amides from alcohols according to: R1-CH2-OH + R2-XH + 2 A ® R1-CO-XR2 + 2 “H2” (X = O, NH).[1] Transition metal complexes with olefins as steering ligands and amido functions as cooperating ligands are remarkable efficient catalysts promoting the DHC of substrates from renewable feedstock with a high turnover frequency and high chemoselectivity. Possible mechanisms will be discussed which inspired the development of an Organometallic Fuel Cell (OMFC)[2] and an efficient catalyst for the conversion of methanol water mixtures into H2 and CO2.

[1] M. Trincado, K. Kühlein, H. Grützmacher, Chem. Eur. J., 2011, 17, 11905-11913.

[2] S. P. Annen, V. Bambagioni, M. Bevilacqua, J. Filippi, A. Marchionni, W. Oberhauser, H.

Schönberg, F. Vizza, C. Bianchini, H. Grützmacher, Angew. Chem. 2010, 7387-7391; Angew.

Chem. Int. Ed. Engl. 2010, 49, 7229-7233.

26

Metal Ligand Cooperation Hansjörg Grützmacher*

aETH, Zürich, Switzerland; bSYSU Lehn Institute of Functional Materials, China


Despite immense progress, bond activation chemistry still requires enormous

research efforts. Even hydrogenation, dehydrogenation, and transfer hydrogenations still need to and can be improved. Most of these processes require noble transition metals. It is desirable to replace these by metal free catalytic systems, or replace noble transition metals by earth abundant ones, or to generate catalytic systems of very high activity and robustness. Metal-ligand cooperation in catalysis can be defined as follows: A

“cooperating ligand” in a transition metal complex participates directly in a bond activation reaction and undergoes a reversible chemical transformation. The metal and

the ligand cooperate in a synergistic manner and their interplay facilitates a chemical process. Because of the polarity bond activation across the metal, M, and ligand, X, vector lead to heterolytic cleavages. This particular property can offer interesting alternatives to existing methods. Alternatively, coordinated radicals can be employed as “cooperating ligands”. Using selected examples from the literature, the principles (as far as they have been explored) and some applications of metal ligand cooperatively will be discussed.

M X M XH2+

– H2

H H

cooperatingligand site

metalcenter

δ+ δ− δ+ δ−

δ+δ− M X•

XY

H

M X

•X YH

H

– Y=Y – 2 H+

– 2e

27

Reactions of Late Transition Metal Alkyl and Hydride Complexes with Molecular Oxygen

Karen I. Goldberg*

University of Washington, Department of Chemistry, Seattle, WA 98195-1700, USA


From environmental and economic standpoints, molecular oxygen represents an

ideal oxidant for chemical transformations. It is readily available, inexpensive (particularly if used without separation from air) and environmentally benign. However, more expensive and/or hazardous oxidants are often employed in oxidation reactions. Further understanding of how transition metal complexes react with molecular oxygen will assist in efforts to develop new selective homogeneous catalytic reactions that effectively utilize this abundant and environmentally friendly oxidant.

One potential high value use of oxygen as an oxidant would be in selective alkane functionalization. A variety of late transition metal complexes have been shown to activate alkane C-H bonds to generate metal alkyl and alkyl hydride complexes. To accomplish alkane functionalization, such late metal species need to undergo further reaction. If oxygen is to be used as an oxidant, the reactivity of these species with oxygen needs to be understood. With this goal in mind, the reactions of a variety of late transition metal alkyls, hydrides and alkyl hydride complexes with molecular oxygen have been investigated. The insertion of oxygen into metal-hydride bonds to form metal-hydroperoxides, the insertion of oxygen into metal-alkyl bonds to form metal-alkylperoxides and oxygen-induced reductive elimination have all been observed. Mechanistic investigations and our nascent understanding of the scope of these oxygen reactions with late transition metal complexes will be presented.

28

Brainstorming New Project Ideas Karen I. Goldberg*

University of Washington, Department of Chemistry, Seattle, WA 98195-1700, USA


The Center for Enabling New Technologies through Catalysis (CENTC), a US

National Science Foundation Center for Chemical Innovation (NSF-CCI) devotes a portion of our annual meeting to brainstorming. During this time, through discussions in small groups, we consider what we have heard earlier in the meeting about the current and future challenges in the chemical industry and propose ideas about how to address these challenges through new catalytic processes. Everything is put forth ranging from we need to think more about reaction chemistry in a broad area (e.g. syngas chemistry) to addressing a particular reaction using a specific catalyst. The discussions in each small group differ dramatically with the participation of individuals from different backgrounds in each group. The larger group then reassembles to share each small group’s best ideas and perspectives. As the last act of this Winter School, we are going to try a similar exercise. You each will have spent the week learning about many different problems and approaches in homogeneous catalysis. Now it is your chance to process some of this information in a new way…thinking about what you and the field can do next. The only rule will be to not be in a group with people you knew before coming to the conference. Diversity makes for the best brainstorming. Enjoy and speak up!

29

Poster Abstracts

30

Poster 1

CaRLa – The Catalysis Research Laboratory Catalyzing the Cooperation Between Science and Industry

Peter Hofmann,a,b* Michael Limbacha,c* aCatalysis Research Laboratory, Im Neuenheimer Feld 584, 69120 Heidelberg, Germany;

bOrganisch-Chemisches Institut der Universität Heidelberg, Im Neuenheimer Feld 270, 69120 Heidelberg,

Germany; cBASF SE, GCS/C – M313, 67056 Ludwigshafen, Germany

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

Innovation is an intersectoral topic. In this regard, public private partnerships are key

instruments for improving a country’s innovativeness. CaRLa is a new role model of research cooperation, in which BASF and the

University of Heidelberg work closely together in a joint laboratory. In CaRLa, 6 postdocs of the university, supervised by Heidelberg faculty, together with 6 postdocs directed by BASF research units are working bench to bench to investigate basic research issues directed towards potential industrial applications in the field of transition metal based homogeneous catalysis. The goal of CaRLa is to facilitate the transfer of results from basic research towards applications in industry.

Catalysis is the most important chemical technology of the chemical industry. More than 80 percent of all chemical products come into contact with catalysts at least once during their synthesis. Research in the field of homogeneous catalysis without doubt has resulted in an exceptional track record of real innovations. Its potential spans a wide range from polymerization to hydroformylation, carbonylation, asymmetric hydrogenation, carbon-carbon or carbon-heteroatom bond formation to applications of homogeneously catalyzed metathesis.

In CaRLa, industry and academia jointly have identified interesting fields of research and challenging targets. CaRLa utilizes the expertise of its principal investigators to optimize a focused research portfolio covering contemporary topics of transition metal based homogeneous catalysis.

31

Poster 2

Picking Boranes with Pincers: A combination of B-H and B-B C-H, and B-C activation and coupling Aviel Anaby,a Moran Feller,a Yehoshoa Ben-David,a Linda J. W. Shimon,b

David Milsteina* aDepartment of Organic Chemistry; bDepartment of Chemical Research Support, The Weizmann Institute

of Science, Rehovot, 76100, Israel


The borane B-H bond was found to add readily to late transition metal pincer

complexes via metal-ligand cooperation. New adduct complexes, some of which consist of the boryl moiety residing on the ligand backbone, were identified and characterized. Furthermore, ruthenium, iridium and rhodium based pincer complexes were found to efficiently catalyze coupling reactions of boranes and arenes, resulting in new boron-carbon bond formation under mild conditions, with molecular hydrogen being the sole by-product. This convenient access to alkyl and aryl borane reagents is highly useful in synthetic organic chemistry, particularly advantageous in hydrocarbon functionalization methodologies.1

[1] Miyaura, N.; Suzuki, A. Chem. Rev. 1995, 95, 2457.

32

Poster 3

Palladium Catalysts for the Synthesis of Sodium Acrylate from CO2 and Ethylene Piyal Ariyananda,a Miriam Bru,a Alvaro Gordillo,a Takeharu Kageyama,a Philipp-

Nikolaus Plessow,a,b Michael Limbacha,b* aCaRLa - Catalysis Research Laboratory, Im Neuenheimer Feld 584, D-69120 Heidelberg, Germany; bBASF SE, Synthesis and Homogeneous Catalysis, GCS/C - M313, Carl-Bosch-Strasse 38, D-67056

Ludwigshafen, Germany


Sodium acrylate is an important bulk chemical to manufacture polyacrylates, which

are used as high performance superabsorbers. Recently, we have disclosed the first catalytic synthesis of sodium acrylate starting from ethylene and CO2 based on a Ni complex.1 Nickelalactones turned out to be key intermediates in this transformation.

We envisage to extend this methodology to Palladium. Nevertheless, so far there has been no precedence of a direct oxidative coupling of CO2 and

ethylene yielding palladalactones. Herein, we present several Pd precursors that enter a Pd-mediated cycle to form sodium acrylate in a stoichiometric reaction via palladalactones.

[1] Lejkowski M.; Lindner, R.; Kageyama, T.; Bódizs, G. E.; Plessow, P. N.; Müller, I. B.; Schäfer,

A.; Rominger, F.; Hofmann, P.; Futter, C.; Schunk, S. A.; Limbach, M. Chem. Eur. J. 2012, 18,

14017-14025.

CO2

ONa

O

tBuOH

PPd

PONa

O

PPd

P

tBu2

tBu2

tBu2

tBu2

PPd

PtBu2

tBu2

O O

NaOtBu

PPd

PtBu2

tBu2

O ONa

O tBu

33

Poster 4

Determining the Enantioselectivity of Racemic Organocatalysts by ESI-MS Screening

Florian Bächle,a Ivana Fleischer,b Andreas Pfaltza*

aUniversity of Basel, St. Johanns-Ring 19, 4053 Basel, Switzerland; bLeibniz Institute for Catalysis,

A.-Einstein-Str. 29a, 18059 Rostock, Germany


Recently, our group developed a new methodology to determine the enan-

tioselectivity of racemic catalysts based on scalemic substrate mixtures1 and the concept of ESI-MS back reaction screening.2 This principle was successfully applied to the Pd-catalyzed allylic alkylation reaction.3 The selectivity of the catalyst was determined based on the monitored intermediate ratio. Here, we present the application of this methodology to the organocatalyzed Michael reaction.

N+

iPr

XN+

Et

X* *(S/R) (R /S)

iPr

CH(COOBn)2

CHO

Et

CH(COOBn)2

CHO

+

75 : 25

NH

XNH

X

perfect enantioselective

catalyst

N+

iPr

XN+

Et

X

50 : 50

50 : 50NH

XNH

X

nonselectivecatalyst

75 : 25

50 : 50

intermediate ratio monitored by ESI-MS

scalemic mixture of mass-labeled

quasi-enantiomeric substrates

[1] Dominguez B.; Hodnett N. S.; Lloyd-Jones G. C., ACIE 2001, 40, 4289-4291.

[2] Müller C. A.; Markert C.; Teichert A. M.; Pfaltz A., Chem. Commun. 2009, 1607-1618.

[3] Ebner C.; Müller C. A.; Markert C.; Pfaltz A., J. Am. Chem. Soc. 2011, 133, 4710-4713.

34

Poster 5

Rhodium-Catalysed Bis-Hydroformylation Reaction of 1,3-Butadiene to Adipic Aldehyde

Bojan P. Bondzic,a Eszter Takács,a Stuart E. Smith,a Peter Hofmanna,b* aCatalysis Research Laboratory (CaRLa), Im Neuenheimer Feld 584, D-69120, Heidelberg, Germany;

bOrganisch-Chemisches Institut, University of Heidelberg, Im Neuenheimer Feld 270, D-69120 Heidelberg,

Germany


Hydroformylation (the “oxo reaction”) is one of the largest homogeneous

transition-metal-catalyzed processes operated industrially.1 Despite the importance and atom economy of the oxo process, the dihydroformylation of conjugated dienes is not a standard reaction.1 For instance, the simplest diene, 1,3-butadiene, typically obtained from large industrial steam-cracking units, can yield up to 14 different aldehydes and their reaction products.

Different reaction conditions and new ligand structures have been examined in the rhodium-catalyzed low-pressure hydroformylation of 1,3-butadiene. The selectivity for the desired linear dihydroformylation product, 1,6-hexanedial (adipic aldehyde), is essentially less dependent of all reaction parameters, than for ligand structure variation. The optimum reaction parameters and ligand structures have so far resulted in a maximum selectivity of 50% for adipic aldehyde.2

[1] Weissermel, K.; Arpe, H.-J. Industrial Organic Chemistry, 4th ed.; Wiley-VCH: Weinheim,

Germany, 2003.

[2] Smith, S. E.; Rosendahl, T.; Hofmann, P. Organometallics, 2011, 30, 3643-3651.

35

Poster 6

Catalytic Formation of Sodium Acrylate from CO2 and Ethylene Miriam Bru,a Alvaro Gordillo,a Piyal Ariyananda,a Ronald Lindner,a Philipp-Nikolaus

Plessow,a,c Michael Limbacha,c* aCaRLa – Catalysis Research Laboratory, Im Neuenheimer Feld 584, D-69120 Heidelberg, Germany; bBASF SE, Synthesis and Homogeneous Catalysis, GCS/C – M313, Carl-Bosch-Strasse 38, D-67056

Ludwigshafen, Germany; cOrganisch-Chemisches Institut Ruprecht-Karls-Universität Heidelberg, Im

Neuenheimer Feld 270, D-69120 Heidelberg, Germany.


Sodium acrylate is an important basic chemical that serves as a monomer for the

synthesis of superabsorbent polymers. The current industrial process is based on a two-step oxidation of propylene. The catalytic synthesis of acrylates from CO2 and ethylene is considered to be a dream reaction. Nickelalactones as reported in the early work of Hoberg1 have been discussed as a possible entry to a catalytic cycle. Herein we present the first catalytic synthesis of sodium acrylate from CO2 and ethylene.2

[1] Hoberg, H.; Peres, Y.; Krüger, C.; Tsay, Y. H. Angew. Chem. Int. Ed. 1987, 26, 771-773.

[2] Lejkowski M.; Lindner, R.; Kageyama, T.; Bódizs, G. E.; Plessow, P. N.; Müller, I. B.; Schäfer,

A.; Rominger, F.; Hofmann, P.; Futter, C.; Schunk, S. A.; Limbach, M. Chem. Eur. J. 2012, 18,

14017-14025.

CO2

ONa

O

R1OH

Ni(COD)2

PR2R2P

dtbpe

PNi

PONa

O

PNi

P

R2

R2

R2

R2

PNi

PR2

R2

O O

NaOR1

PNi

PR2

R2

O ONa

OR1

36

Poster 7

The Design of Palladium (II) Methanesulfonate Precatalysts for C-C, CN and C-N Cross-Coupling Reactions

Nicholas C. Bruno, Stephen L. Buchwald*

Massachusetts Institute of Technology, USA


A series of easily prepared, phosphine-ligated palladium (II) precatalysts based on

the 2-aminobiphenyl scaffold have been synthesized. The role of the precatalyst-associated halide or pseudohalide in the formation and stability of the palladacycle has been examined. It was found that replacing the chloride in the previous version of the precatalyst with methanesulfonate leads to a new class of precatalysts with improved solution stability that are readily prepared from a much wider range of phosphine ligands. Structural differences in the solid state between the previous version of precatalyst and the palladium methanesulfonate precatalysts are explored. In addition, the reactivity of the latter is examined in a range of C–C, C-O, and C–N bond forming reactions.1

[1] Bruno, N. C,; Tudge, M. T.; Buchwald S. L Chem. Sci. 2012, Advance Article.

37

Poster 8

Gold Vinylidenes in Catalysis Janina Bucher, A. Stephen K. Hashmi*

Organisch-Chemisches Institut, Ruprecht-Karls-Universität Heidelberg, Im Neuenheimer Feld 270, 69120

Heidelberg, Germany


The most common reactivity pattern in the field of homogeneous gold catalysis is the

inter- or intramolecular attack of a nucleophile onto a multiple bond which is activated

as an electrophile by π-coordination of a gold complex. Herein, we report on a new activation mode which comprises a dual role of the gold

catalyst: In the cyclisation of aromatic diynes, a terminal triple bond is activated by

σ-coordination of a gold complex. This formation of a gold(I) acetylide causes an umpolung reactivity and enables the alkyne to react as a nucleophile. Attack via its

β-carbon atom onto the other alkyne unit which is electrophilically activated by π-coordination of a second molecule of gold catalyst leads to highly reactive gold vinylidene intermediates II. These are able to undergo CH-activation processes of unactivated C(sp2)-H and even C(sp3)-H bonds and therefore open up entirely new reaction pathways.1-3

[1] Ye, L.; Zhang, L. J. Am. Chem. Soc. 2012, 134, 31-34.

[2] Hashmi, A. S. K.; Braun, I. Organometallics 2012, 31, 644-661.

[3] Hashmi, A. S. K.; Wieteck, M. Angew. Chem. Int. Ed. 2012, 51, 10633-10637.

38

Poster 9

Studies into Ullmann Kinetics and Development of a Beneficial Slow-Addition Procedure

Robert Cox, Guy Lloyd-Jones*

University of Bristol, UK


Formation of the biaryl ether moiety remains a challenging target for organic

synthesis despite modern technologies, however, better understanding of older techniques often leads to improvements. The copper-catalysed Ullmann ether synthesis, whilst attactive in many ways, is frequently problematic due to the inherent irreproducibility of the reaction on scale up. Little is yet known about the mechanism of the reaction and conflicting views are rife within the scientific community.1

In a well studied example,2 we show that the potassium iodide formed during the

reaction slows catalysis. Additionally, the deprotonation of phenol 2 is complicated by the insolubility of the inorganic base. This results in a beneficial outcome, providing a rate enhancement and reduction of by-products which can be further exploited to provide lower stoichiometries, improved selectivity and greater functional group tolerance.

[1] Sperotto, E., van Klink, G. P. M., van Koten, G., de Vries, J. G., Dalton Trans. 2010, 39,

10338-10351.

[2] Tye, J., Weng, Z., Giri, R., Hartwig, J. F., Angew. Chem. Int. Ed. 2010, 49, 2185–2189.

39

Poster 10

Highly Enantioselective Copper-Catalyzed Electrophilic Trifluoromethylation of β-Ketoesters

Qing-Hai Deng,a,b Hubert Wadepohl,b Lutz H. Gadea,b*

aCatalysis Research Laboratory (CaRLa), Im Neuenheimer Feld 584, 69120 Heidelberg, Germany; bAnorganisch-Chemisches Institut, Universität Heidelberg, Im Neuenheimer Feld 270, 69120 Heidelberg,

Germany


Using previously developed chiral pincer ligands,1 we report Cu-catalyzed

enantioselective trifluoromethylations of β-ketoesters using commercially available trifluoromethylating reagents.2 A number of α-CF3 β-ketoesters are obtained with up to 99% ee. The trifluoromethylated products were then transformed diastereospecifically to α-CF3 β-hydroxyesters with two adjacent quaternary stereocenters via Grignard reaction.

[1] Deng, Q.-H.; Wadepohl, H.; Gade, L. H. Chem. Eur. J. 2011, 17, 14922; Deng, Q.-H.;

Wadepohl, H.; Gade, L. H. J. Am. Chem. Soc. 2012, 134, 2946.

[2] Deng, Q.-H.; Wadepohl, H.; Gade, L. H. J. Am. Chem. Soc. 2012, 134, 10769.

40

Poster 11

Copper-Mediated Fluorination of Aryl Iodides and Arylboronate Esters Patrick S. Fier, John F. Hartwig*

Department of Chemistry, University of California, Berkeley, California 94720, USA


The synthesis of aryl fluorides has been studied intensively because of the

importance of aryl fluorides in materials and biologically active molecules. Recently, transition metals have been used to form aryl fluorides, and these reactions offer mild alternatives to the Balz-Schiemann and Halex reactions. However, before our work, the direct conversion of aryl halides and aryl-boron reagents to aryl fluorides had not been developed. We have designed a readily available copper reagent, (tBuCN)2CuOTf, which mediates the fluorination of unactivated aryl iodides with AgF.1 These reactions occur with good substrate scope and represent the only examples for the fluorination of unactivated aryl halides. In addition, (tBuCN)2CuOTf mediates the fluorination of arylboronate esters with an electrophilic fluorinating reagent under mild reaction conditions.2 The fluorination of arylboronate esters is complementary to the fluorination of aryl iodides, in part, because catalytic reactions which form arylboronate esters in-situ can be used in one-pot, two-step fluorinations of arenes and aryl bromides. A series of mechanistic studies were performed on these two fluorination reactions. Our data support reaction mechanisms in which the fluoroarenes are formed by reductive elimination from aryl-Cu(III)-fluoride species.

[1] Fier, P. S.; Hartwig, J. F. J. Am. Chem. Soc. 2012, 134, 10795.

[2] Fier, P. S.; Luo, J.; Hartwig, J. F. J. Am. Chem. Soc. 2013, 135, ASAP.

41

Poster 12

FhuA-based hybrid catalysts for selective transformations Steve Gotzen,a Freddi Philippart,a Claudio Broglia,a Joana Tenne,b Marcus Arlt,b Marco

Bocola,b Uli Schwaneberg,b* Jun Okudaa*

aInstitute of Inorganic Chemistry, RWTH Aachen University, Landoltweg 1, 52074 Aachen Germany; bInstitute of Biotechnology, RWTH Aachen University, Worringerweg 1, 52074 Aachen, Germany

e-mail: [email protected]*

Regio- and stereoselective transformations could be developed by new types of hybrid catalysts (artificial metalloenzymes), consisting of a protein backbone including an active metal center connected by a linking unit.1 Using the large cavity within an

engineered β-barrel membrane protein, FhuA ∆1-1592 as the protein part and a Grubbs-Hoveyda type catalyst as the chemical part new types of hybrid catalysts have been designed. This FhuA variant, containing one single cysteine at amino acid position 545, was linked to a cysteine selective functional group by dative anchoring. These new hybrid catalysts were found to be active in ring-opening metathesis polymerization in aqueous solutions.

[1] Steinreiber, J.; Ward, T. R. Coord. Chem. Rev. 2008, 252, 751.

[2] Onaca, O.; Sakar, P.; Roccatano, D.; Friedrich, T.; Hauer, B.; Grzelakowski, M.; Güven, A.;

Fioroni, M.; Schwaneberg, U. Angew. Chem. Int. Ed. 2008, 47, 7029.

42

Poster 13

BAr4F as Counteranion in Intermolecular Gold(I)-Catalyzed Reactions Anna Homs, Carla Obradors, David Leboeuf, A. M. Echavarren*

Institute of Chemical Research of Catalonia (ICIQ), Spain


In the last decade, gold complexes have emerged as exceptional catalysts for the

activation of alkynes, alkenes and allenes giving access to a wide range of novel transformations.1 Since the first report of an intermolecular gold-catalyzed cyclization involving alkynes in 2010,2 several new intermolecular reactions have seen the light. However, one major drawback with these cyclizations is the formation of alkynyl-digold species, which are in equilibrium with the active (η-alkyne)gold complex and can prevent the reaction.3

During our studies, we discovered that the counteranion employed with gold(I) complexes has a strong influence on the reactivity. Thus, we prepared a new generation of gold(I) complexes using BAr4

F as counteranion, which led to higher yields in intermolecular reactions in shorter reaction times. Kinetic studies have been performed to explain this counteranion effect in the formation of the aforementioned alkynyl-digold complexes.

[1] Gorin, D. J.; Sherry, B. D.; Toste, F. D. Nature 2007, 446, 395; Jiménez-Núñez, E.;

Echavarren, A. M. Chem. Rev. 2007, 107, 333; Rudolph, M.; Hashmi, A. S. K. Chem.

Commun. 2011, 47, 6536.

[2] López-Carrillo, V.; Echavarren, A. M. J. Am. Chem. Soc. 2010, 132, 9292-9294.

[3] Brown, T. J; Wiedenhoefer, R. A. Organometallics 2011, 11, 6003-6009.

43

Poster 14

Boraindenes and the Activation of Small Molecules Adrian Y. Houghton,a Virve A. Karttunen,b Warren E. Piers,a* Heikki M. Tuonnonenb* aDepartment of Chemistry, University of Calgary, 2500 University Drive NW, Calgary, Alberta, Canada

T2N 1N4; bDepartment of Chemistry, University of Jyväskylä, P.O. Box 35, FI-40014 Jyväskylä, Finland


The five-membered unsaturated boracycles known as boroles are highly Lewis acidic,

display interesting electronic properties and are formally anti-aromatic.1-3 A particularly interesting feature of some boroles is the ability to activate dihydrogen at ambient temperature and pressure,4,5 which is surprising in light of the fact that boron-based Lewis acids typically require the presence of a bulky base to accomplish this.6 However, the activation of dihydrogen by boroles is irreversible, and so to achieve reversible dihydrogen activation we have endeavoured to synthesize a new class of boroles: boraindenes. Herein we report the synthesis and characterization of novel boraindenes as well as their reactivity towards dihydrogen and other small molecules.

[1] Eisch, J. J.; Hota, N. K.; Kozima, S. J. Am. Chem. Soc. 1969, 91, 4575-4577.

[2] Braunschweig, H.; Kupfer, T. Chem. Commun. 2011, 47, 10903-10914.

[3] Fan, C.; Piers, W. E.; Parvez, M. Angew. Chem. Int. Ed. 2009, 48, 2955-2958.

[4] Fan, C. J. Am. Chem. Soc. 2010, 132, 9604-9606.

[5] Houghton, A. Y. J. Am. Chem. Soc. 2012, 135 (2), 941-947.

[6] Stephan, D. W.; Erker, G. Angew. Chem. Int. Ed. 2010, 49, 46-76.

44

Poster 15

Insight into Hydrogenation Catalysis: An Investigation of CO2 and Carbonyl Compound Activation by a Ru Pincer Complex

Chelsea A. Huff, Melanie S. Sanford*

University of Michigan, 930 N. University, Ann Arbor, MI 48109, USA


CO2 is an abundant, renewable C1 building block that has the potential to be utilized

in the synthesis of many commodity chemicals and fuels that are currently derived from fossil feedstocks. Methanol is a leading commodity chemical, produced annually on a multimillion metric ton scale, primarily from synthesis gas. We established a system that directly hydrogenates CO2 to methanol through a cascade of homogeneously catalyzed reactions.1 Herein, we investigate potential side reactions and decomposition pathways involving one component of our cascade system, a Ru pincer complex, and we apply these findings to hydrogenation catalysis. [1] Huff, C.A.; Sanford, M. S. J. Am. Chem. Soc. 2011, 133, 18122-18125.

45

Poster 16

β-Keto Heteroarylsulfones: Versatile Nucleophiles in Asymmetric Organocatalysis Christian Borch Jacobsen, Karl Anker Jørgensen*

Center for Catalysis, Department of Chemistry, Aarhus University, Denmark


The utilization of β-keto heteroarylsulfones as nucleophiles in asymmetric

organocatalytic reactions has allowed us to construct a range of one-pot protocols, leading to the formation of elusive enantioenriched products (Figure).1 Among other notable results,2 this has made it possible to develop the first catalytic asymmetric β-alkynylation of α,β-unsaturated aldehydes2a and the first asymmetric monofluorovinylation.2c

This poster will focus on the ability of these nucleophiles to function as versatile reaction partners in the

construction of new enantioenriched molecules, and the underlying mechanistic aspects.

[1] For a review see e.g. Nielsen, M.; Jacobsen, C. B.; Holub, N.; Paixão, M. W.; Jørgensen, K. A.

Angew. Chem. Int. Ed. 2010, 49, 2668-2679.

[2] a) Nielsen, M.; Jacobsen, C. B.; Paixão, M. W.; Holub, N.; Jørgensen, K. A. J. Am. Chem. Soc.

2009, 131, 10581-10586. b) Jacobsen C. B.; Lykke L.; Monge, D.; Nielsen M.; Ransborg, L.

K.; Jørgensen, K. A. Chem. Commun. 2009, 6554-6556. c) Jacobsen, C. B.; Nielsen, M.;

Worgull, D.; Zweifel, T.; Fisker, E.; Jørgensen, K. A. J. Am. Chem. Soc. 2011, 133, 7398-7404.

d) Jacobsen, C. B.; Jensen, K. L.; Udmark, J.; Jørgensen, K. A. Org. Lett. 2011, 13,

4790-4793.

Figure. Examples of the products obtained by using

β-keto heteroarylsulfones in organocatalytic one-pot

protocols. Het = heteroaryl, PG = protection group.

46

Poster 17

Development of Cationic Ruthenium Carbene Complexes Incorporating Bidentate NHCP Ligands

Christopher Brown,a Phillip Jolly,a Kristina Wilckens,a Hiyam Salem,a Martin Schmitt,b Erik Kühnel,b Marcel Brill,b Philipp Nägele,b Frank Rominger,b Peter Hofmanna,b*

aCatalysis Research Laboratory (CaRLa), University of Heidelberg, Im Neuenheimer Feld 584, D-69120

Heidelberg, Germany; bOrganisch-Chemisches Institut, University of Heidelberg, Im Neuenheimer Feld

270, D-69120 Heidelberg, Germany


Olefin metathesis has become a general tool for the construction of carbon-carbon

bonds. Since the first Grubbs-type catalysts many Ru olefin metathesis catalysts have been prepared. Hofmann and co-workers reported cationic ruthenium carbene complexes based on the ligands dtbpm and dtbpe. They show exceptionally high activity in ROMP, even at ppm-range catalyst concentrations.1 In light of the high activity of these complexes and the advantages which NHCs displayed for 2nd generation Grubbs catalysts, our recently developed bidentate phosphine-functionalized NHC ligands2 (NHCP) have been applied to Ru with an aim towards catalytic olefin metathesis. The results presented herein will demonstrate initial coordination chemistry and preliminary catalytic screening.

[1] Volland, M. A. O.; Hansen, S. M.; Rominger, F.; Hofmann, P. Organometallics 2004, 23, 800.

[2] Salem, H.; Schmitt, M.; Herrlich, U.; Kühnel, E.; Brill, M.; Nägele, P.; Bogado, A. L.;

Rominger, F.; Hofmann, P. Organometallics 2013, 32, 29; Nägele, P.; Herrlich, U.; Rominger,

F.; Hofmann, P. Organometallics 2013, 32, 181.

47

Poster 18

Selective Functionalizations of Diazines and Benzo Analogues Thomas Klatt,a Klaus Groll,a Daniela Sustac Roman,b Paul Knochela*

aLudwig-Maximilians-Universität München, Department Chemie, Germany; bCentre in Green Chemistry

and Catalysis, Université de Montréal, Canada


Due to their potential biological properties, the access to functionalized

heteroaromatics is of high importance. The regioselective functionalization by direct metalation has proven to be an excellent tool for this purpose. The sterically hindered bis(trimethylsilyl)methyl group allows the regioselective magnesiation of pyrazines using the frustrated Lewis pair BF3·OEt2 and TMP2Mg·2LiCl.1 Full functionalization of the pyrazine core is achieved by further metalations with TMP2Mg·2LiCl.2

This metalation protocol can be extended to benzo diazines such as cinnolines.

Regioselective magnesation with TMP2Mg·2LiCl occurs in position 3. Complimentary, the milder base TMP2Zn·MgCl2·2LiCl3 which is generated in situ metalates the cinnoline in position 8.

[1] Jaric, M.; Haag, B. A.; Unsinn, A.; Karaghiosoff, K.; Knochel, P. Angew. Chem. Int. Ed. 2010,

49, 5454.

[2] Clososki, G. C.; Rohbogner, C. J.; Knochel, P. Angew. Chem. Int. Ed. 2007, 46, 7681.

[3] Wunderlich, S. H.; Knochel, P. Angew. Chem. Int. Ed. 2007, 46, 7685.

48

Poster 19

Regiodivergent Reductive Coupling of 2-Substituted Dienes to Formaldehyde Employing Nickel or Ruthenium Catalyst

Alexander Köpfer,a Brannon Sam,b Bernhard Breit,a* Mike Krischeb*

aAlbert-Ludwigs-Universität Freiburg, Albertstrasse 21, 79104 Freiburg, Germany; bUniversity of Texas

at Austin, Austin, TX 78712, USA

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

Whilst rhodium catalyzed alkene hydroformylation is highly efficient, the

corresponding reaction with 1,3-dienes generally suffers from low regioselectivity and the formation of double hydroformylation byproducts.

We developed reductive couplings of 2-substituted 1,3-butadienes to formaldehyde

employing a Nickel or Ruthenium catalysts to access coupling at all four positions selectively. iPrOH or formaldehyde itself serves as mild reductant via transfer hydrogenation.1 [1] Köpfer, A.; Sam, B.; Breit, B.; Krische, M. J. Chem. Sci. 2013, accepted.

49

Poster 20

Dual Catalytic Enantioselective Allylation of α–Branched Aldehydes Using Combined Iridium and Enamine Catalysis

Simon Krautwald, David Sarlah, Michael A. Schafroth, Erick M. Carreira*

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


Combined organic and transition metal catalysis can be a powerful tool for developing otherwise

difficult asymmetric reactions.[1] Herein, we describe a dual catalytic enantioselective method for the

direct allylation of α-branched aldehydes.[2] The overall transformation is effected through Ir-catalyzed

allylic substitution of racemic allylic alcohols with enamines that are generated catalytically from

aldehydes and cinchona-alkaloid derived primary amines.[3] This method gives access to all four possible

stereoisomers in good yields and with excellent selectivities by using either enantiomer of ligand 1 in

combination with either pseudoenantiomer of 2.

[1] For a review, see: Zhong, C.; Shi, X. Eur. J. Org. Chem. 2010, 2999.

[2] For a seminal report on dual organo/transition metal catalyzed allylation, see: Ibrahim, I.;

Córdova, A. Angew. Chem., Int. Ed. 2006, 45, 1952.

[3] For an example of the use of stoichiometric amounts of enamines in Ir-catalyzed allylic

substitution, see: Weix, D.; Hartwig, J. F. J. Am. Chem. Soc. 2007, 129, 7720.

50

Poster 21

Direct Aldol Polymerization of Acetaldehyde Shuhei Kusumoto, Shingo Ito, Kyoko Nozaki*

Department of Chemistry and Biotechnology, Graduate School of Engineering, The University of Tokyo,

Japan

[email protected]

Since vinyl alcohol does not exist as an enol form, current industrial process for producing poly(vinyl alcohol)s employs vinyl acetate, a protected form of vinyl alcohol, for its radical polymerization and the following removal of the protecting groups. Although repetitive aldol addition of acetaldehyde, the keto form of vinyl alcohol, would achieve the direct one-step synthesis of poly(vinyl alcohol)s, it remained one of the biggest challenges in polymer chemistry. Inspired by the recent developments in organocatalytic transformations, we investigated the direct aldol reaction of acetaldehyde by organocatalysis. Thus, we successfully synthesized poly(vinyl alcohol)-type oligomers by using a combination of pyrrolidinyltetrazole and Brönsted acids as catalysts. NMR analyses revealed that the obtained acetaldehyde oligomer I consists of hydroxyethylene units, acetal of 1,3-diol units, and ethynylene units formed by dehydration. The following hydrogenation and deacetalization afforded oligomer II corresponding to poly(ethylene-co- vinyl alcohol)-type oligomer.

H

O(5 mmol)

acid (5 mmol)

H2O (1 mL)rt, 7 days

OH O O O

H(100 mL)

NH

NH

NNN

Mn = 200~800selectivity = 3~23%

1) Pd/C, H2, MeOH 90% yield

2) Pd(OH)2, MeOH 30% yield

OH OH

H

oligomer I oligomer IIx y z

x:y:z ≈ 4:5:3

x+2y z

51

Poster 22

From Homogeneous to Heterogeneous Catalysts: Recyclable and Selective Catalytic Systems for the Synthesis of Poly(silyl ether)s

Guillermo Lázaro, Manuel Iglesias, Eugenio Vispe, Francisco J. Fernández-Alvarez,* Jesús J. Pérez-Torrente, Luis A. Oro*

Departamento de Química Inorgánica - ISQCH, Universidad de Zaragoza – CSIC, Spain


Poly(silyl ether)s represent a family of promising degradable polymeric materials

because of their hydrolytic reactivity.1 These polymers have been obtained by metal-catalyzed hydrosilylation using [Ru(CO)H2(PPh3)3] as catalyst precursor.2

The economic viability of a chemical process is directly related to the selectivity and recyclability of the corresponding catalyst. This fact is increasing the interest in the immobilization of selective homogeneous catalysts into solid supports, thus producing heterogeneous catalysts which would maintain the selectivity of the homogeneous catalytic system and be easily recycled.3 Here, the synthesis and characterization of new Rh(I)-NHC complexes containing a doubly functionalized NHC ligand is reported. These new Rh(I)-NHC species were immobilized on MCM-41, KIT-6 and Aerosil to obtain their heterogeneous analogous. The activity of the new heterogeneous catalytic systems in the synthesis of poly(silyl ether)s by Rh-catalyzed hydrosilylation has comparatively been studied. [1] Li, Y.; Seino, M.; Kawakami, Y. Macromolecules 2000, 33, 5311-5314.

[2] Mabry, J. M.; Runyon, M. K.; Weber, W. P. Macromolecules 2002, 35, 2207-2211.

[3] Rothenberg, G., In Catalysis: Concepts and Green Applications; Wiley-VCH: Weinheim,

2008.

52

Poster 23

Metal Catalysts in Biomass Conversion Claudia Loerbroks, Qiong Tong, Ferdi Schüth,* Walter Thiel*

Max-Planck-Institut für Kohlenforschung, Kaiser-Wilhelm-Platz 1, D-45470 Mülheim an der Ruhr,

Germany


Recent energy shortages have led to an increased interest in renewable energy

sources like biomass. One interesting target for biomass conversion is 5-hydroxymethylfurfural (HMF), which is an intermediate of the biofuel dimethylfuran (Scheme).1 In this study we investigate one step of the conversion process: the isomerisation of glucose (1) to fructose (2), using density functional theory (DFT, PBE0/6-31+G**).

Scheme. Formation of 5-hydroxymethylfurfural from glucopyranose.

Experimentally, the reaction from 1 to 2 was carried out in water at 120°C with and without metal catalysts. While Cr3+ and Al3+ perform well, Fe3+ and Mg2+ proved less or not active.2 The goal of this study is to compare the uncatalysed reaction with the catalysed one and to find the reason for the different reactivities. [1] Rosatella, A. A. Green Chem. 2011, 13, 754-793.

[2] Private communication.

53

Poster 24

Asymmetric Counteranion-Directed Hosomi-Sakurai Reaction Manuel Mahlau, Pilar García-García, Benjamin List*

Max-Planck-Institut für Kohlenforschung, Kaiser-Wilhelm-Platz 1, 45470 Mülheim an der Ruhr,

Germany


Asymmetric allylation reactions are amongst the most useful reactions in organic

synthesis and have been used to evaluate the potential of catalysts and catalytic concepts for asymmetric synthesis. The development of enantioselective Lewis-acid catalysts faces the problem of non-enantioselective TMS+ catalysis after initial activation by the chiral Lewis-acid.1 Our group has developed the concept of asymmetric counteranion-directed catalysis (ACDC).2 The underlying idea is to use ion-pairing between a cationic reaction intermediate or transition state and a chiral counteranion to induce enantioselection. We recently extended the applicability of this concept to organo-Lewis-acid catalysis using chiral disulfonimide catalysts.3 Here we report an enantioselective Hosomi-Sakurai allylation of aromatic aldehydes.

[1] T. K. Hollis, B. Bosnich, J. Am. Chem. Soc. 1995, 117, 4570.

[2] For reviews, see: M. Mahlau, B. List, Isr. J. Chem. 2012, 52, 630; R. J. Phillips, G.. L.

Hamilton , F. D. Toste, Nature Chem. 2012, 4, 603; M. Mahlau, B. List, Angew. Chem. Int. Ed.

2013, 52, 518; K. Brak, E. N. Jacobsen, Angew. Chem. Int. Ed. 2013, 52, 534.

[3] P. García-García, F. Lay, P. García-García, C. Rabalakos, B. List, Angew. Chem. Int. Ed. 2009,

48, 4363; L. Ratjen, P. García-García, F. Lay, M. E. Beck, B. List, Angew. Chem. Int. Ed.

2011, 50, 754; J. Guin, C. Rabalakos, B. List, Angew. Chem. Int. Ed. 2012, 51, 8859; M.

Mahlau, P. Gracía-Gracía, B. List Chem. Eur. J. 2012, 18, 16283.

54

Poster 25

Saturated Abnormal NHC-Gold(I) Complexes: Synthesis and Catalytic Activity

Rubén Manzano,a Dominic Riedel,b A. Stephen K. Hashmia,b*

aCatalysis Research Laboratory, Im Neuenheimer Feld 584, 69120 Heidelberg, Germany; bOrganisch-Chemisches Institut, Im Neuenheimer Feld 270, 69120 Heidelberg, Germany


The interest in the synthesis of N-heterocyclic carbene complexes (NHCs) with

reduced heteroatom stabilization1 has increased in the last years. In contrast to normal NHCs, the abnormal NHCs (aNHCs) bear the metal at a carbon atom in the two-carbon tether (C4, C5) and not at the carbon atom between the two nitrogen atoms (C2). Here we report the regioselective [3+2]-cycloaddition of azomethine ylides and isonitrile gold(I) complexes,2 which gives easy access to a variety of saturated abnormal carbene gold(I) complexes. The procedure tolerates substituents at both nitrogen atoms as well as at the carbon atom which neighbors the carbene position. These compounds have been tested as catalysts, after activation with a silver salt, in model reactions.

[1] Schuster, O.; Yang, L.; Raubenheimer, H. G.; Albrecht, M. Chem. Rev. 2009, 109, 3445;

Albrecht, M. Chem. Commun. 2008, 3601; Arnold, P. L.; Pearson, S. Coord. Chem. Rev. 2007,

251, 596.

[2] Manzano, R.; Rominger, F.; Hashmi, A. S. K., submitted; Hashmi, A. S. K.; Riedel, D.;

Rudolph, M.; Rominger, F.; Oeser, T. Chem. Eur. J. 2012, 18, 3827.

55

Poster 26

Ruthenium phenyl indenyl complex as efficient catalyst for transfer hydrogenation, oxidation and isomerisation reactions

Simone Manzini,a César A. Urbina-Blanco,a Albert Poater,b Alexandra M. Z. Slawin,a Luigi Cavallo,c Steven P. Nolana*

aEaStCHEM School of Chemistry, University of St Andrews, United Kingdom; bInstitut de Química

Computacional, Departament de Química, University of Girona, Spain; cDepartment of Chemistry and

Biology, University of Salerno, Italy


The stability in alcohol solution of the well-defined and easily accessed

[RuCl2(PPh3)2(3-phenylindenylidene)] (M10) complex was studied. 1 showed an interesting rearrangement of the indenylidene moiety to form a novel complex [RuCl(PPh3)2(3-phenylindenyl)] (1).1 1 has been revealed to be a active catalyst in redox and

isomerisation reactions, especially in racemisation of chiral alcohols at very low loadings,1 and

isomerisation of allylic alcohol to ketones at room temperature. Moreover, 1 is active in transfer

hydrogenation reactions, surpassing the commonly used ruthenium catalysts,2 and is

chemoselective in the oxidation of secondary alcohols3.

[1] Manzini, S.; Urbina-Blanco, C. A.; Poater, A.; Slawin, A. M. Z.; Cavallo, L.; Nolan, S. P.,

Angew. Chem., Int. Ed. 2012, 51, 1042-1045.

[2] Manzini, S.; Urbina-Blanco, C. A.; Nolan, S. P. Adv. Synth. Catal. 2012, 354, 3036-3044.

[3] Manzini, S.; Urbina-Blanco, C. A.; Nolan, S. P. Organometallics 2013,

DOI:10.1021/om301156v.

56

Poster 27

Total Synthesis of Bioactive Marine Diterpenes Using a Co-Catalyzed Hydrovinylation on the Basis of Modular Chiral P,P-Ligands

Sohajl Movahhed, Hans-Günther Schmalz*

Department für Chemie, Cologne, Germany


In our group a modular synthesis has been developed that provides access

to a broad variety of chiral phosphine-phosphite ligands which proved to be highly active in asymmetric metal catalysis.1 In the context of the recently published total synthesis of Helioporin C and E the asymmetric induction was achieved via a Cu(I)-catalyzed allylic alkylation in the presence of chiral P,P-ligands yielding an enantiomeric excess of up to 99%.2

Such P,P-ligands are now being investigated in the Co-catalyzed hydrovinylation reaction within the scope of a short and diversity oriented total synthesis of the structurally related and highly biologically active marine diterpenes Pseudopterosin (A-Z).

[1] A. Falk, A.-L. Göderz, H.-G. Schmalz Angew. Chem. Int. Ed. 2013, 52,

1576-1580; M. Dindaroğlu, A. Falk, H.-G. Schmalz Synthesis 2013, ASAP.

[2] W. Lölsberg; S. Werle; J.-M. Neudörfl; H.-G. Schmalz Org. Lett. 2012, 14,

5996-5999.

57

Poster 28

C-H Bond Activation of Heteroaromatics and Internal Alkynes and Their Application for End-functionalized Polymerization of 2-Vinylpyridine by Yttrium

Alkyl Complex Haruki Nagae, Hiroshi Kaneko, Hayato Tsurugi, Kazushi Mashima*

Department of Chemistry, Graduate School of Engineering Science, Osaka University, Japan


Well-defined polymers with end-capping groups having a different polarity and

reactivity from the backbone are attracting scientific and industrial interest for their application as building blocks and additives in the construction of new functional materials. We anticipated that the combination of the living coordination-polymerization of vinyl monomers and the C-H bond activation reactions, which produced the catalysts bearing any terminal functional group, provided such the end-functionalized polymer without any sequential reactions. Herein, we demonstrated the end-functionalized polymerization of 2-vinylpyridine (2-VP) by yttrium catalysts derived by C-H bond activation of N-heteroaromatic compounds and internal alkyne with a yttrium-alkyl complex 1.1

[1] Kaneko, H.; Nagae, H.; Tsurugi, H. Mashima, K. J. Am. Chem. Soc. 2011, 133, 19626.

58

Poster 29

Iron-Catalyzed Intramolecular Allylic C—H Amination Shauna M. Paradine, M. Christina White*

Department of Chemistry, University of Illinois, Urbana, Illinois 61801, USA


Nitrogen functionality is prevalent in biologically active molecules, but is often

challenging to introduce and carry through syntheses. C−H amination represents a powerful means of rapidly introducing nitrogen into complex molecules, obviating the need to carry these sensitive groups through multiple manipulations and streamlining synthetic efforts. Toward this end, we have developed the first general C—H amination reaction under iron catalysis, which employs an inexpensive, non-toxic [FeIIIPc] catalyst.1 [FeIIIPc] is highly chemo- and site-selective, displaying a strong preference for allylic C—H amination over aziridination and amination of all other C—H bond types (i.e. allylic > benzylic > ethereal > 3° > 2° >> 1°). Further, observed reactivity trends are orthogonal to those observed under rhodium catalysis. In polyolefinic substrates, site selectivities for [FeIIIPc]–catalyzed C—H amination can be controlled by the electronic and steric character of the allylic C—H bond. Although this reaction is shown to proceed via a stepwise mechanism, mechanistic studies also suggest a very rapid radical rebound step.

[1] Paradine, S. M.; White, M. C. J. Am. Chem. Soc. 2012, 134, 2036-2039.

59

Poster 30

Mechanistic Details of the Formation of Methyl Acrylate from CO2, Ethylene and Methyl Iodide

Philipp Pleßow,a,b Laura Weigel,c Ronald Lindner,b Ansgar Schäfer,a Michael Limbach,b Peter Hofmannb,c*

aBASF SE, Quantum Chemistry, GVM/M – B009, Carl-Bosch-Strasse 38, D-67056 Ludwigshafen,

Germany; bCaRLa (Catalysis Research Laboratory), Im Neuenheimer Feld 584, D-69120 Heidelberg,

Germany; cRuprecht-Karls-Universität Heidelberg, Organisch-Chemisches Institut, Im Neuenheimer Feld

270, D-69120 Heidelberg, Germany


Methyl iodide allows for nickel mediated stoichiometric formation of free methyl

acrylate from carbon dioxide and ethylene via nickelalactones.1 We explore possible mechanisms of this reaction by theoretical and experimental means. The calculated elementary steps agree well with experimental findings. We were able to isolate reactive intermediates and to verify the existence of proposed reaction pathways. Our results differ substantially from a recently proposed mechanism.2 We have furthermore identified possible mechanisms for side reactions. With suitable bases, side reactions

can be suppressed and acrylate π-complexes can be synthesized stoichiometrically. The strong binding of Methyl acrylate to nickel is with the spectator ligands applied so far currently preventing a catalytic reaction.

[1] Bruckmeier, C.; Lehenmeier, M. W.; Reichardt, R.; Vagin, S.; Rieger, B.; Organometallics

2010, 29, 2199.

[2] Lee, S. Y. T.; Cokoja, M.; Drees, M.; Li, Y.; Mink, J.; Herrmann, W. A.; Kuehn, F. K.

ChemSusChem 2011, 4, 1275–1279.

60

Poster 31

N-Heterocyclic carbenes as organocatalysts for the hydroacylation of alkenes Michael Schedler, Duo-Sheng Wang, Frank Glorius*

Organisch-Chemisches Institut, Westfälische Wilhelms-Universität Münster

Corrensstraße 40, 48149 Münster, Germany


Based on our recent findings that a highly electron-rich 2,6-dimethoxyphenyl

substituent increases the reactivity and selectivity of N-heterocyclic carbenes (NHC)1 as organocatalysts in hydroacylation reactions of electron-neutral but strained alkenes,2 we synthesized a family of NHCs with this new substituent.3 These new catalysts enable the use of NHCs as catalyst for the intermolecular hydroacylation of simple alkenes, namely styrenes.4 This transformation uses abundant starting materials as aldehydes and styrenes and yields under mild conditions valuable ketone structures. A series of aromatic aldehydes and eight electron-deficient styrenes reacted nicely to the wanted products; additionally electron-neutral and electron-rich styrenes could be used under slightly modified conditions. Changing the electronic parameters of the starting materials had a strong influence of the regioselectivity of the reaction and hence gave interesting information on the mechanism of this transformation.

[1] D. Enders, O. Niemeier, A. Henseler, Chem. Rev. 2007, 107, 5606; X. Bugaut, F. Glorius,

Chem. Soc. Rev. 2012, 41, 3511.

[2] F. Liu, X. Bugaut, M. Schedler, R. Fröhlich, F. Glorius, Angew. Chem. Int. Ed. 2011, 50,

12626; Angew. Chem. 2011, 123, 12834.

[3] M. Schedler, R. Fröhlich, C. G. Daniliuc, F. Glorius, Eur. J. Org. Chem. 2012, 4164.

[4] M. Schedler, D.-S. Wang, F. Glorius, Angew. Chem. Int. Ed. 2013, 52, in press. (Hot paper)

61

Poster 32

Synthesis of Di- and Tridentate Phosphinomethylamine Ligands, Their Coordina-tion Chemistry and Application in Asymmetric Catalysis

Peter Scherl, Achim Kruckenberg, Julio Lloret Fillol, Steffen Mader, Hubert Wadepohl, Lutz H. Gade*

Anorganisch-Chemisches Institut, Universität Heidelberg, Germany


We have developed a highly modular synthesis of di- and tridentate phospholanome-

thylamine ligands which we have employed in the rhodium catalyzed asymmetric hy-drogenation of olefins, yielding excellent enantioselectivities.1

Furthermore, an achiral tridentate model ligand was prepared which formed a ruthe-nium η

4-trimethylenemethane (tmm) complex upon reaction with [Ru(COD)(methylallyl)2]. Likewise, a C3-symmetric ruthenium tmm complex contain-ing a chiral trisphospholane was obtained.2 [1] Lloret Fillol, J.; Kruckenberg, A.; Scherl, P.; Wadepohl, H.; Gade, L. H. Chem. Eur. J. 2011,

17, 14047-14062.

[2] Scherl, P.; Kruckenberg, A.; Mader, S.; Wadepohl, H.; Gade, L. H. Organometallics 2012, 31,

7024-7027.

62

Poster 33

Uranium-Mediated Reductive Conversion of CO2 to CO and Carbonate in a Single-Vessel Closed Synthetic Cycle Anna-Corina Schmidt, Karsten Meyer*

Department of Chemistry and Pharmacy, Inorganic Chemistry, Friedrich-Alexander-University of

Erlangen-Nuremberg, Egerlandstr. 1, 91058 Erlangen, Germany


In our efforts to utilize small molecules of industrial and biological relevance, we

have turned our attention to the activation of carbon dioxide at uranium coordination complexes. Employing the latest generation complex, it was shown that [((Np,MeArO)3tacn)U] – in the presence of an atmosphere of CO2 and excess reductant (KC8) – converts CO2 to CO and K2CO3 in a single-vessel, closed synthetic cycle.1 However, the reaction is terminated prematurely upon formation of an insoluble, polynuclear U-carbonate; which precipitates and thus limits its catalytic application.

[1] Schmidt, A.-C.; Nizovtsev, A.V.; Scheurer, A.; Heinemann, F.W.; Meyer, K. Chem. Comm.

2012 , 48, 8634-8636.

63

Poster 34

Rh-catalyzed Hydroformylation of 1,3-Butadiene - Illuminating the Mechanism with Experiment and Theory

Sebastian Schmidt,a Golnar Abkai,a Frank Rominger,a Peter Hofmanna,b*

aUniversity of Heidelberg, INF 270, D-69120 Heidelberg, Germany; bCatalysis Research Laboratory

(CaRLa), INF 584, D-69120 Heidelberg, Germany


The selective bis-hydroformylation of 1,3-butadiene to adipic aldehyde is one of the

so-called "dream reactions" in industry. However, control of the regioselectivity remains an unsolved problem even though many highly selective catalysts for hydroformylation of monoalkenes have been found.

+ +2 H2 2 CO[Rh/L] H

H

O

O

Recently, unprecedentedly high selectivities of up to 50 % adipic aldehyde were obtained with our new family of TTP-type bisphosphite ligands.1,2 Higher selectivities seem to be within reach via a more rational ligand design, but require a more profound knowledge about the mechanism.

We combine theoretical (DFT) with experimental (in situ IR and NMR spectroscopy, kinetics, model complexes, isotopic labeling) investigations to further improve our understanding of the catalysts and their activity and selectivity.

[1] S. Smith, T. Rosendahl, P. Hofmann, Organometallics 2011, 30, 3643-3651.

[2] W. Ahlers, M. Röper, P. Hofmann, D. C. M. Warth, R. Paciello, WO 01/58589 A1, 2001; W.

Ahlers, R. Paciello, M. Röper, P. Hofmann, M. Tensfeldt, A. Goethlich, WO 01/85739 A1,

2001; W. Ahlers, R. Paciello, D. Vogt, P. Hofmann, WO 02/083695 A1, 2002.

64

Poster 35

Triarylmethyl Palladium Complexes as Potential Catalysts Stephan Schöler, Arik Puls, Nicole Wurster, Maike Wahl, Gerald Dyker*

Fakultät Chemie Ruhr-Universität Bochum Universitätsstr. 150 D-44780 Bochum, Germany


Two types of potential new catalysts are introduced, combining the redoxactive

nature of the triarylmethyl (trityl) ligand with a Pd(II) salt: in the cyclometallated complexes of type 1 the metal center is covalently bound to the triarylmethyl carbon and coordinated by an ortho-functionality, contrasting the bonding situation as well as the macroscopic solubility of the parent structure, originally studied by Sonoda et al.[1]

In the chiral complexes of type 2 the metal center is connected with the trityl moiety by an imidoyl linkage. Anisotropic effects of the Pd(II) center effect a downfield-shift of selected aromatic protons in the 1H NMR to about 11 ppm.

SR

PdCl

ONO

NOCH3

OCH3

2

PdCl

Cl

R

1

R'

R''

[1] A. Sonoda, B. E.Mann, P. E. Maitlis, J. Chem. Soc., Chem. Commun., 1975, 108-9; A. Sonoda,

B. E.Mann, P. E. Maitlis, J. Chem. Soc., Dalton Trans., 1979, 346-50.

65

Poster 36

Nickel-Catalyzed Synthesis of Diarylamines via Oxidatively Induced C–N Bond Formation

Matsubara Tatsuaki, Ilies Laurean, Nakamura Eiichi*

Department of Chemistry, Graduate School of Science, The University of Tokyo, Japan


Nickel-catalyzed C–N bond formation has been much less explored compared with

the extensively investigated C–C bond formation. The main reason is that reductive elimination to give a C–N bond is more difficult because of the high electronegativity of the nitrogen atom, and therefore sophisticated ligands and harsh reaction conditions have been typically required.

I report herein a nickel-catalyzed oxidatively induced C–N bond formation, where reductive elimination readily proceeds from a high-valent-nickel center at room temperature.1 Primary amines react with Grignard reagents in the presence of an oxidant and a catalytic amount of nickel to give diarylamines selectively. The reaction proceeds without the assistance of an external ligand, and halide, ester, and ketone groups are tolerated.

Mechanistic studies suggest that the reductive elimination proceeds from a high-valent-nickel species such as Ni(III) that is obtained by oxidation via single electron transfer. This reaction is rare example of nickel-catalyzed oxidatively induced C–N bond formation.2

[1] Ilies, L.; Matsubara, T.; Nakamura, E. Org. Lett. 2012, 14, 5570–5573.

[2] Hickman, A. J.; Sanford, M. S. Nature, 2012, 484, 177–185.

66

Poster 37

Implication of ligand protonation in asymmetric hydrogenation Frédéric G. Terrade,a A. M. Kluwer,b R. J. Detz,b Joost N. H. Reeka,b*

aVan ‘t Hoff Institute for Molecular Sciences, Faculty of Science, University of Amsterdam, Science park

904, 1098 XH Amsterdam, The Netherlands; bInCatT B.V., Science Park 904, 1098 XH Amsterdam, The

Netherlands


The METAMORPhos family is a new class of Brønsted acidic sulfonamide-phosphorus ligands. Upon coordination with rhodium 1 gave the unique complexes 4 consisting of two metal centers and four identical ligands: two P-N bridging and two P-O chelating ligands.1 4 shows unprecedented activity and stereoselectivity for the hydrogenation of challenging substrates (cyclic enamides 5).

Recent spectroscopic observations and X-ray studies revealed that the chelate ligands

of 4 are deprotonated both in the crystal state and in solution by triethylamine. Indeed, the coordination of ligand 2 leads to the same dimeric complexes. However, the catalytic activity and the selectivity drops when this proton free system is used.

The addition of a weak acid to the catalytic mixture enhances both activity and enantioselectivity. Initial kinetic studies suggest that without additive, the rate equation follows a first order in substrate (which is intuitive and commonly observed), but in the presence of the weak acid, the rate equation follows a second order in substrate.

[1] F. Patureau, S. De Boer, M. Kuil, J. Meeuwissen, P.-A. Breuil, M. Siegler, A. Spek, A. Sandee,

B. De Bruin, J. N. H. Reek, J. Am. Chem.Soc. 2009, 131, 6683-6685

67

Poster 38

TADDOL-related Phosphoramidites as Efficient Ligands for Asymmetric Gold-Catalysis

Henrik Teller, Matthieu Corbet, Luca Mantilli, Dieter Weber, Alois Fürstner*

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


To comprehensively apply gold(I)-catalysis in natural product synthesis, the

development of efficient asymmetric transformations is mandatory. Gold(I), however, poses a particular challenge in this regard: it favors a linear dicoordination geometry. This intrinsic attribute of gold(I) restricts not only chelation of the metal center by commonly used asymmetric bidentate ligands, but it also places the stereo-inducing chiral information trans to the substrate binding site, sandwiching the bulky metal center, which often inhibits efficient stereocontrol over an outer-sphere nucleophilic attack.1

The Fürstner group demonstrated that monodentate TADDOL-related phosphoramidites are efficient ligands for [2+2] and [4+2] cycloadditions of ene-allenes, cycloisomerizations of enynes, hydroarylation reactions with formation of indolines, as well as intramolecular hydroaminations and hydroalkoxylations of allenes.2 Their preparative relevance is underscored by the total synthesis of the antidepressive drug (–)-GSK 1360707.3

[1] Pradal, A.; Toullec, P. Y.; Michelet, V. Synthesis 2011, 1501.

[2] Teller, H.; Corbet, M.; Mantilli, L.; Gopakumar, G.; Goddard, R.; Thiel, W.; Fürstner, A. J. Am.

Chem. Soc. 2012, 134, 15331; Teller, H.; Flügge, S.; Goddard, R.; Fürstner, A. Angew. Chem.

Int. Ed. 2010, 49, 1949.

[3] Teller, H.; Fürstner, A. Chem.–Eur. J. 2011, 17, 7764.

68

Poster 39

Cp*Ir(III)-Complexes: Active Catalysts in the Alkylation of Amines with Alcohols Simone Wöckel,a,c Eric J. Derrah,a,c Frank Rominger,b Peter Hofmann,a,b Michael

Limbacha,c*

aCaRLa – Catalysis Research Laboratory, Im Neuenheimer Feld 584, D-69120 Heidelberg, Germany; bOrganisch-Chemisches Institut, Ruprecht-Karls-Universität Heidelberg, Im Neuenheimer Feld 270,

D-69120 Heidelberg, Germany; cBASF SE, Synthesis & Homogeneous Catalysis, Carl-Bosch-Strasse 38,

D-67056 Ludwigshafen, Germany


Amines are of great industrial interest as starting materials or intermediates.1 The

metal-catalyzed alkylation of amines with alcohols via a hydrogen borrowing

mechanism has become an outstanding reaction since alcohols are readily available and the only byproduct is water.2 Although iridium-based homogeneous catalysts have been reported in this context,3 those systems require harsh reaction conditions. We will present iridium-based complexes that are active without additives, work under mild conditions and yield secondary amines in high selectivity.4

[1] Bähn, S.; Imm, S.; Neubert, L.; Zhang, M.; Neumann, H.; Beller, M. ChemCatChem 2011, 3,

1853-1864.

[2] Balcells, D.; Nova, A.; Clot, E.; Gnanamgari, D.; Crabtree, R. H.; Eisenstein, O.

Organometallics 2008, 27, 2529-2535.

[3] See for example: Fujita, K.-i.; Yamamoto, K.; Yamaguchi, R. Org. Lett. 2002, 4, 2691-2694.

[4] Wetzel, A.; Wöckel, S.; Schelwies, M.; Brinks, M. K.; Rominger, F.; Hofmann, P.; Limbach,

M. Org. Lett. 2013, 5, 266 – 269

69

Poster 40

Palladium-Catalysed Direct Polyarylation of Pyrrole Derivatives Liqin Zhao, Christian Bruneau,* Henri Doucet*

Institut Sciences Chimiques de Rennes, UMR 6226, CNRS-Universite de Rennes 1 “Organometalliques:

Materiaux et Catalyse”, Campus de Beaulieu, 35042 Rennes, France


For palladium-catalysed direct arylation of pyrroles, the most reactive positions are

the carbons C2 and C5, whereas the positions C3 and C4 display a poor reactivity.1 The palladium-catalysed direct polyarylation of 1-methylpyrrole and 1-phenylpyrrole was studied. The formation of 2,5-diarylpyrroles was found to proceed selectively in the presence of 3 equiv. of a variety of aryl bromides. The sequential C2 arylation followed by C5 arylation to prepare non-symmetrically substituted 2,5-diarylpyrroles was also studied. The tetraarylation of 1-methylpyrrole was also achieved.2 The major by-products of these reactions are a base associated to HBr, and the method avoids the preparation of a (poly)organometallic.

[1] Campeau, L.-C.; Stuart, D. R.; Fagnou, K. Aldrichimica Acta 2007, 40, 35; Bellina, F.; Rossi,

R. Tetrahedron 2009, 65, 10269; Ackermann, L.; Vicente, R.; Kapdi, A. Angew. Chem. Int. Ed.

2009, 48, 9792; Roger. J.; Gottumukkala. A.L.; Doucet. H. ChemCatChem. 2010, 2, 20.

[2] Zhao, L.; Bruneau, C.; Doucet H. ChemCatChem 2013, 5, 255.

70

Poster 41

Fixation of CO2 and N2O by frustrated Lewis pairs Eileen Theuergarten, Danny Schlüns, Constantin G. Daniliuc, Matthias Tamm*

Technische Universität Carolo-Wilhelmina Braunschweig, Institut für Anorganische und Analytische

Chemie, Germany


Lately, the activation of small molecules, in particular dihydrogen, by frustrated

Lewis pairs became a prospering area of research.1 The borane Lewis acid B(C6F5)3 in combination with sterically demanding five- membered N-heterocyclic carbenes present an intermolecular frustrated Lewis pair, which affords the ring opening reaction of THF and splits dihydrogen heterolytically.2 Further investigations were done on the activation of carbon dioxide and nitrous oxide in formation of the expected adducts.

Recently, the synthesis of the intramolecular pyrazolborane frustrated Lewis pair was published. Besides the heterolytic activation of dihydrogen,3 this FLP system was also employed for the fixation of carbon dioxide. DFT calculations revealed, that the formation of the expected adduct is strongly exothermic and proceeds with a low energy barrier of approximately 7.3 kcal mol-1.4

[1] A. L. Kenward, W. E. Piers, Angew. Chem. Int. Ed. 2008, 47, 38-41; D. W. Stephan, G. Erker,

Angew. Chem. Int. Ed. 2010, 49, 46-76.

[2] D. Holschumacher, T. Bannenberg, C. G. Hrib, P. G. Jones, M. Tamm, Angew. Chem. Int. Ed.

2008, 47, 7428-7432; S. Kronig, E. Theuergarten, D. Holschumacher, T. Bannenberg, C. G.

Daniliuc, P. G. Jones, M. Tamm, Inorg. Chem. 2011, 50, 7344-7359.

[3] E. Theuergarten, D. Schlüns, J. Grunenberg, C. G. Daniliuc, P. G. Jones, M. Tamm, Chem.

Commun. 2010, 46, 8561-8563.

[4] E. Theuergarten, J. Schlösser, D. Schlüns, M. Freytag, C. G. Daniliuc, P. G. Jones, M. Tamm,

Dalton Trans. 2012, 41, 9101-9110.

71

Lecturer

Lutz Ackermann

Georg-August-Universität Göttingen

Institut für Organische und Biomolekulare

Chemie

Tammannstrasse 2

37077 Göttingen, Germany

[email protected]

Friedhelm Balkenhohl

BASF SE

Synthesis & Homogeneous Catalysis (GCS)

– M313

67056 Ludwigshafen, Germany

[email protected]

Gerhard Erker

Universität Münster

Institut für Organische Chemie

Corrensstr. 40

48149 Münster, Germany

[email protected]

Lutz H. Gade

Anorganisch-Chemisches Institut

Universität Heidelberg

Im Neuenheimer Feld 270

69120 Heidelberg, Germany and

CaRLa - Catalysis Research Laboratory



[email protected]

John A. Gladysz

Department of Chemistry

Texas A&M University

College Station, TX 77843-3255, USA

[email protected]

Karen I. Goldberg


University of Washington

Box 351700

Seattle, WA 98195-1700, USA

[email protected]

Alan S. Goldman

Rutgers, the State University of New Jersey

Department of Chemistry & Chemical

Biology

Wright-Rieman Laboratories, Office 180

610 Taylor Road, Piscataway, NJ 08854,

USA

[email protected]

Hansjörg Grützmacher

Laboratorium für Anorganische Chemie

Wolfgang-Pauli-Str. 10

ETH Hönggerberg,

HCI H 131

8093 Zürich, Switzerland [email protected]

E. Peter Kündig

Department of Organic Chemistry

University of Geneva - Sciences II

30, quai Ernest-Ansermet

1211 Geneva 4, Switzerland

[email protected]

Rocco Paciello

BASF SE

Synthesis & Homogeneous Catalysis

(GCS/H) – M313

67056 Ludwigshafen, Germany

[email protected]

T. Don Tilley


University of California, Berkeley

Berkeley, CA 94720-1460, USA

[email protected]

72

mailto:[email protected]


http://wwwuv2.uni-muenster.de/uniplan/?action=spot&gebnr=1171#x








Participants

Aviel Anaby

The Weizmann Institute of Science

76100 Rehovot, Israel

[email protected]

Piyal Ariyananda

Catalysis Research Laboratory (CaRLa)



[email protected]

Florian Bächle

Universität Basel

Departement Chemie

Organische Chemie

St. Johanns-Ring 19

CH-4056 Basel

Switzerland

[email protected]

Bojan Bondzik




[email protected]

Christopher Brown




[email protected]

Miriam Bru




[email protected]

Nick Bruno

Massachusetts Institute of Technology

Room 18-490

77 Massachusetts Avenue

Cambridge, MA 02139, USA

[email protected]

Janina Bucher

Organisch-Chemisches Institut

Ruprecht-Karls-Universität Heidelberg



[email protected]

Robert Cox

School of Chemistry

University of Bristol

Cantock's Close

Bristol, BS8 1TS, UK

[email protected]

Qinghay Deng




[email protected]

Eric Derrah




[email protected]

Patrick Fier

University of California


718 Latimer Hall MC #1460

Berkeley, CA 94720-1460, USA

[email protected]

Alvaro Gordillo




[email protected]

Steve Gotzen

Institut für Anorganische Chemie

RWTH Aachen

52056 Aachen, Germany

[email protected]

73















A. Stephen K. Hashmi





[email protected]

Peter Hofmann

Institute of Organic Chemistry

University of Heidelberg


69120 Heidelberg, Germany and




[email protected]

Anna Homs

Institute of Chemical Research

of Catalonia (ICIQ)

Av. Països Catalans 16

E-43007 Tarragona, Spain

[email protected]

Adrian Houghton


University of Calgary

2500 University Dr. NW

Calgary, Alberta, Canada T2N 1N4

[email protected]

Chelsea Huff

University of Michigan


930 N. University

Ann Arbor, MI 48109-1055, USA

[email protected]

Christian Borch Jacobsen

Center for Catalysis

Department of Chemistry, Aarhus University

Langelandsgade 140

DK-8000 Aarhus C, Denmark

[email protected]

Philipp Jolly




[email protected]

Thomas Klatt

Department Chemie und Biochemie

Ludwig-Maximilians-Universität

Butenandtstraße 5-13

81377 München, Germany

[email protected]

Simon Krautwald

ETH Zürich

Laboratory of Organic Chemistry

HCI H335

Wolfgang-Pauli-Strasse 10

8093 Zürich

Switzerland

[email protected]

Alexander Köpfer

Institut für Organische Chemie & Biochemie

Albert-Ludwigs-Universität Freiburg

Albertstrasse 21a

79104 Freiburg i. Brsg., Germany

[email protected]

Shuhei Kusumoto

Department of Chemistry and Biotechnology

School of Engineering

The University of Tokyo

7-3-1 Hongo, Bunkyo-ku

113-8656 Tokyo, Japan

[email protected]

Michael Limbach

BASF SE

Synthesis & Homogeneous Catalysis

(GCS/C) – M313

67056 Ludwigshafen, Germany and




[email protected]

Claudia Loerbroks

Max-Planck-Institut für Kohlenforschung

Kaiser-Wilhelm-Platz 1

45470 Mülheim an der Ruhr, Germany

[email protected]

74













Manuel Mahlau




[email protected]

Ruben Manzano




[email protected]

Simone Manzini

School of Chemistry

Purdie Building, room 343

North Haugh

University of St Andrews

St Andrews, KY16 9ST, UK

[email protected]

Tatsuaki Matsubara


School of Science, The University of Tokyo

Hongo, Bunkyo-ku

Tokyo 113-0033, Japan

[email protected]

Sohajl Movahhed

Universität zu Köln

Institut für Organische Chemie

Greinstrasse 4

50939 Köln, Germany

[email protected]

Haruki Nagae


Graduate School of Engineering Science

Osaka University

Toyonaka, Osaka 560-8531, Japan

[email protected]

Shauna M. Paradine


University of Illinois

270 Roger Adams Laboratory

600 South Mathews Ave.

Urbana, IL 61801, USA

[email protected]

Philipp Plessow




[email protected]

Michael Schedler

Westfälische Wilhelms-Universität Münster


Corrensstrasse 40

48149 Münster, Germany

[email protected]

Peter Scherl

Anorganisch-Chemisches Institut




[email protected]

Hubert Schmidbaur

Department Chemie der Technischen

Universität München

Lichtenbergstraße 4

85747 Garching, Germany

[email protected]

Ana-Corina Schmidt

Friedrich-Alexander-Universität Erlangen-

Nürnberg

Lehrstuhl für Anorganische und Allgemeine

Chemie

Egerlandstraße 1

91058 Erlangen, Germany

[email protected]

Sebastian Schmidt





[email protected]

Stephan Schöler

Fakultät Chemie

Ruhr-Universität Bochum

Universitätsstr. 150

44780 Bochum, Germany

[email protected]

75














Frederic Terrade

University of Amsterdam

Van 't Hoff Institute for Molecular Sciences

Science Park 904

1098 XH Amsterdam, The Netherlands

[email protected]

Eileen Theuergarten

TU Braunschweig

Hagenring 30

38106 Braunschweig, Germany

[email protected]

Guillermo Lazaro Villarroya

Instituto Universitario de Catálisis

Homogénea

Department of Inorganic Chemistry

I.C.M.A.- Faculty of Science

University of Zaragoza-CSIC

Zaragoza-50009, Spain

[email protected]

Dieter Weber




[email protected]

Simone Wöckel




[email protected]

Liqin Zhao

Université de Rennes1

Sciences Chimiques de Rennes

Campus de Beaulieu

Avenue du général Leclerc

35042 Rennes cedex, France

[email protected]

76







Your way to the conference venue: dai

Deutsch Amerikanisches Institut (dai) Sofienstrasse 12 69115 Heidelberg

From Hotel Europäischer Hof

From Exzellenzhotel/Boardinghouse

distance: about 450 meters (5 minutes to walk)

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6th carla winter school 2013...

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