CaRLa Winter School 2008carla-hd.de/wp-content/uploads/2018/02/CaRLaWinterSchool...overwhelming interest in their organic applications has tended to overshadow their inorganic reaction

5th CaRLa Winter School

2012 Heidelberg

March 3-9, 2012

Final Program

Welcome to the 5th 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 March 3-9, 2012 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 and 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, 3rd March until 16:00 Arrival and Coffee Break 16:30 Welcome Address Thomas Rausch

Prorector of Ruprecht Karls University, Heidelberg

17:00 Key Note Lecture “Raw Material Change in the Chemical Industry” Friedhelm Balkenhohl, BASF SE

18:00 Light Dinner and “Get-together”

Sunday, 4th March 9:00 Training Session: Bond Activation with Perfluoroaryl Boranes – Frustrated Lewis

Pairs and Catalysis

(Warren E. Piers)

10:00 Coffee Break

10:15 Lecture: Activation of CO and CO2 with Decamethylscandocinium-hydridoborate

Ion Pairs

(Warren E. Piers)

11:15 Coffee Break

11:30 Flash Poster Presentations

12:00 Lunch Break (free time)

14:30 Lecture: Sustainable and Atom-Efficient Catalytic Routes to Amines

(Dieter Vogt)

15:30 Coffee Break

15:45 Training Session: Ligand Control in Homogeneous Catalysis – The Molecular

Machinery at Work

(Dieter Vogt)

16:45 Coffee Break


17:30 Poster Session including light dinner

Monday, 5th March

9:00 Lecture: The Ruthenium Chemistry of Olefin Metathesis

(Deryn E. Fogg)

10:00 Coffee Break

10:15 Training Session: Sustainable Metathesis

(Deryn E. Fogg)

11:15 Coffee Break



14:30 Lecture: Rational Ligand Design

(Bernd Straub)

15:30 Coffee Break

15:45 Training Session: Pitfalls in the Quantum-chemical Modelling of Catalytic Cycles

(Bend Straub)

16:45 Coffee Break



Tuesday, 6th March

9:00 Lecture: Well-defined supported catalysts via the controlled functionalization of

surfaces

(Christophe Copéret)

10:00 Coffee Break

10:15 Training Session: Support effects in single-site catalysts: A molecular point of

view

(Christophe Copéret)

11:15 Coffee Break



14:30 Lecture: Designing of Catalysts for Stereoregular Polymerization of Propylene

(Mosher Kol)

15:30 Coffee Break

15:45 Training Session: Development of Catalysts for the Synthesis of Poly(Lactic Acid)

and Related Materials

(Moshe Kol)

16:45 Coffee Break



Wednesday, 7th March

9:00 Lecture: Zinc Cluster Catalyzed Transesterification and Oxazoline Synthesis

(Kazushi Mashima)

10:00 Coffee Break

10:15 Training Session: Salt-free Reduction of Tantalum and Tungsten Halides for

Generating Low-valent Catalytically Active Species

(Kazushi Mashima)

11:15 Coffee Break



14:30 Training Session: Industrial Bioprocesses - Basic Principles

(Klaus Ditrich)

15:30 Coffee Break

15:45 Lecture: ChiProsTM - Optically Active Intermediates on an Industrial Scale

(Klaus Ditrich)

16:45 Coffee Break



Thursday, 8th March 9:00 Lecture: Palladium- and Nickel-Catalyzed Cross-Coupling Reactions of Alkyl

Electrophiles

(Gregory C. Fu)

10:00 Coffee Break

10:15 Training Session: Enantioselective Nucleophilic Catalysis

(Gregory C. Fu)

11:15 Coffee Break



14:30 Transfer to Ludwigshafen

15:00 Excursion of BASF’s Main Site in Ludwigshafen

19:00 Winter School Dinner in “Kulturbrauerei”

Friday, 9th March 9:00 Lecture: Adding Aliphatic C—H Bond Oxidations to Synthesis

(M. Christina White)

10:00 Coffee Break

10:15 Training Session: C—H Oxidations and Organic Synthesis (M. Christina White)

11:15 Coffee Break

11:30 Poster Prize Ceremony & Closing Remarks

12:00 Departure

Lectures & Training Sessions

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.

Bond Activation with Perfluoroaryl Boranes—Frustrated Lewis Pairs and Catalysis

Jay Dutton, Adrian Y. Houghton, Adam Marwitz, Matt Morgan, Warren E. Piers,*a and Masood Parvez,a

aDepartment of Chemistry, University of Calgary, 2500 University Drive NW, Calgary, Alberta, T2N

1N4 Canada.

e-mail: [email protected]

The activation of small molecules by Lewis acid/Lewis base combinations that form

very weak classical adducts is a recently exploited phenomenon in main group element chemistry.[1] Because they don’t quench each other through classical adduct formation, they are known as “frustrated Lewis pairs”. This session will describe our group’s contributions to the development of FLP’s and what is known regarding their mechanism of action. Specifically, the role of Lewis acid strength in the reaction will be discussed and methods of assessing Lewis acid strength will be presented. Finally, the state of the art in FLP mediated catalysis will be surveyed.

[1] Stephan, D. W.; Erker, G. Angew. Chem. Int. Ed. 2010, 49, 46-77.

Activation of CO and CO2 with Decamethylscandocinium-hydridoborate Ion Pairs Andreas Berkefeld,a Warren E. Piers,*a Masood Parvez,a Ludovic Castro,b Laurent

Maron,b and Odile Eisensteinc

aDepartment of Chemistry, University of Calgary, 2500 University Drive NW, Calgary, Alberta, T2N

1N4 Canada; bLPCNO, Université de Toulouse, INSA, UPS, LPCNO, 135 avenue de Rangueil, F- 31077

Toulouse, France, and CNRS, LPCNO, F-31077 Toulouse, France ; cInstitut Charles Gerhardt, Université

Montpellier 2, CNRS 5253, cc 1501, Place E. Bataillon, F-34095 Montpellier France


As we have seen, “frustrated Lewis pairs” essentially provide a confined space

within which strong bonds can be activated with very low barriers. In some instances, the components of the activated bond can be transferred to external substrates to close a catalytic cycle, but these examples are relatively narrow in scope. Contact ion pairs comprised of organotransition metal cations and weakly coordinating anions are similar in character to these so-called FLPs, wherein the confined space between the ions may possibly be utilized to activate small molecules. By analogy to the FLP systems, the cation functions as the Lewis acid and the anion functions as the Lewis base; we postulated that the potential for catalytic turnovers from such systems will be enhanced due to the greater variety of reaction manifolds available to transition metals as opposed to main group Lewis acids. We report here the use of the ion pair [Cp*2Sc]+[HB(C6F5)3]- for the activation of CO and CO2. In the case of CO2, highly active catalysts for the hydrosilation of CO2 to CH4 are obtained, while for CO, novel reactivity patterns for coordinated CO are described. The mechanisms of both of these reactions were probed experimentally and computationally and the results of these studies will be described.

Sustainable and Atom-Efficient Catalytic Routes to Amines Dieter Vogt*

Technische Universiteit Eindhoven, Postbus 513, 5600 MB Eindhoven, The Netherlands e-mail: [email protected]

Recent advances in the Rh-catalyzed hydroaminomethylation reaction (HAM), a

one-pot cascade of hydroformylation, condensation with an amine, and hydrogenation towards amines, will be reported. Efficient catalyst and product separation can be achieved by a two-phase approach using ionic liquids.[1],[2]

Furthermore, the highly efficient and selective Ru-catalyzed direct amination of secondary (bio)alcohols with ammonia[3] towards primary amines will be discussed. In this “hydrogen shuttling” approach protective groups are avoided and no additional hydrogen is needed. [1] B. Hamers, P. S. Bäuerlein, C. Müller, D. Vogt, Adv. Synth. Catal. 2008, 350, 332-

342. [2] B. Hamers, E. Kosciusko-Morizet, C. Müller, D. Vogt, ChemCatChem 2009, 1,

103-106. [3] D. Pingen, C. Müller, D. Vogt, Angew. Chem., Int. Ed. 2010, 49, 8130-8133.

mailto:[email protected]

Ligand Control in Homogeneous Catalysis – The Molecular Machinery at Work Dieter Vogt*

Technische Universiteit Eindhoven, Postbus 513, 5600 MB Eindhoven, The Netherlands e-mail: [email protected]

In this session the major concepts and models used in homogeneous catalysis will be

discussed on the basis of selected practical examples and assignments, in which the different concepts are at work in an “as-pure-as-possible” way. The scope and limitations of models will be discussed. Attention will be paid to the delicate interplay of all kind of factors that influence the activity, selectivity and stability of homogeneous catalysts. Examples will come from the literature and from own research. An important aspect of this session will be the way and the means employed to gain insight into the mechanisms of homogeneous catalytic systems.


The Ruthenium Chemistry of Olefin Metathesis Deryn E.Fogg*

Department of Chemistry, and Center for Catalysis Research & Innovation, University of Ottawa, Ottawa

ON, Canada K1N 6N5


Ruthenium metathesis catalysts are now widely recognized as powerful agents for

further, non-metathetical transformations.[1] In some cases, this expanded reactivity is due to the action of the precatalyst and/or its alkylidene and/or methylidene derivatives: in others, it reflects the operation of further ruthenium catalysts generated in situ, whether by chance or design.[2] While a greater understanding of the underlying inorganic transformations of these important complexes would clearly be advantageous, overwhelming interest in their organic applications has tended to overshadow their inorganic reaction chemistry. Many of their fundamental reactivity patterns thus remain obscure. We will examine such pathways as they relate to inhibition or expansion of opportunities in olefin metathesis.

[1] a) Alcaide, B.; Almendros, P.; Luna, A. Chem. Rev. 2009, 109, 3817-3858. b)

Alcaide, B.; Almendros, P. Chem. Eur. J. 2003, 9, 1259-1262. [2] For tandem catalysis originating in metathesis catalysts, see: a) Shindoh, N.;

Takemoto, Y.; Takasu, K. Chem. Eur. J. 2009, 15, 12168-12179. b) Fogg, D. E.; dos Santos, E. N. Coord. Chem. Rev. 2004, 248, 2365-2379. c) Wasilke, J.-C.; Obrey, S. J.; Baker, R. T.; Bazan, G. C. Chem. Rev. 2005, 105, 1001-1020.

Sustainable Metathesis Deryn E Fogg*

Department of Chemistry, and Center for Catalysis Research & Innovation, University of Ottawa, Ottawa

ON, Canada K1N 6N5


Olefin metathesis is attracting expanding interest as a means of harnessing renewable

resources. In particular, metathetical degradation of unsaturated plant oils has long been regarded as a potential "alternative" route to α-olefin feedstocks relevant to commodity chemical applications. A major challenge, however, can be competing degradation of the catalyst itself. We will examine the opportunities and limitations associated with use of "functional-group tolerant" late-metal catalysts in these contexts.

Well-defined supported catalysts via the controlled functionalization of surfaces Christophe Copéret*

Department of Chemistry, ETH Zürich, W. Pauli Strasse, 10 CH-8093 Zürich, Switzerland


Controlling the chemistry at the surface of oxide materials has been a challenge for

forty years. In the first part of this lecture, we will discuss how it is possible to control the OH density of the surface of silica and to exploit these surface functionalities to generate well-defined surface metal complexes, which can then be used as precursor to supported single-site catalysts.[1] We will then discuss the limitation of this approach, and propose to extend it to developing silica supports with regularly distributed surface organic functionalities, which correspond to the typical ligands of organometallic and coordination chemistry.[2] We will also discuss how solid-state NMR spectroscopy enables a detailed understanding of the structure of surface species in relation to their catalytic performances.[3] The lecture will end with an open discussion on problems and solutions. [1] a) Copéret et al. Angew. Chem. Int. Ed. 2003, 42, 156. b) Copéret C. Dalton Trans.

2007, 5498. c) Gajan et al. New. J. Chem. 2011, 35, 2403. [2] a) Maishal et al. Angew. Chem. Int. Ed. 2008, 47, 8654. b) Karamé et al. Chem. Eur.

J. 2009, 15, 11820. c) Baffert et al. ChemSusChem. 2011, 4, 1762. [3] a) Blanc et al. Coord. Chem. Rev. 2008, 37, 518. b) Gajan et al. Manuscript in

preparation.

Support effects in single-site catalysts: A molecular point of view Christophe Copéret*

Department of Chemistry, ETH Zürich, W. Pauli Strasse 10 CH-8093 Zürich, Switzerland


While the first lecture focused on silica-based materials, the second one will try to

elaborate on support effects in heterogeneous catalysis. In particular, it is well known that changing the support from silica to alumina often significantly improved catalyst performances of supported single-site catalysts for the hydrogenation, the metathesis and the polymerization of alkenes.[1] The discussion will thus focus on understanding what is alumina, in particular its surface functionalities as a function of thermal treatment using probe molecules in a combined experimental and first principle calculation approach. The nature and the role of surface functionalities will be discussed in relation to the formation and the stabilization of surface – active – species.[2] The lecture will end with an open discussion on the so-called support effects in heterogeneous catalysis.

[1] Rascon et al. Chem. Sci. 2011, 2, 1449. [2] a) Wischert et al. Chem. Commun., 2011, 47, 4890. b) Wischert et al. Angew. Chem.

Int. Ed., 2011, 50, 3202. c) Wischer et al. submitted.

Designing of Catalysts for Stereoregular Polymerization of Propylene Moshe Kol*

School of Chemistry, Tel Aviv University, Ramat AvivTel Aviv 69978, Israel


Salalens are tetradentate dianionic sequential {ONN’O}-type ligands that include

amine and imine internal neutral donors, and two peripheral anionic phenolate arms. With the imine-donor and the amine-donor orienting their two neighboring donors in meridional and facial geometries, respectively, the Salalens give rise to octahedral complexes of group 4 metals of the type [{ONN’O}MX2] having a fac-mer geometry and C1-symmetry. In such complexes, the two monodentate labile groups are cis-related, and reside in different steric and electronic environments.

We have recently developed an efficient methodology for the synthesis of Salalen ligands that enables the fine-tuning of steric and electronic parameters. We found that several titanium complexes of these ligands led to highly active catalysts for polymerization of α-olefins, and, most importantly, to polypropylene with very high isotacticities, reaching [mmmm] > 99.6% and melting transitions of up to 169.9 °C, which is unprecedented, to our knowledge.[1],[2]

In this presentation we will describe the design principles that have led to this development, and, as time allows, we will describe the breadth of the Salalen ligand family, and the performance of Salalen complexes of other metals in propylene polymerization. [1] Press, K.; Cohen, A.; Goldberg, I.; Venditto, V.; Mazzeo, M.; Kol, M. Angew. Chem.

Int. Ed. 2011, 50, 3529. [2] Sita, L. R. Angew. Chem. Int. Ed. 2011, 50, 6963.

Development of Catalysts for the Synthesis of Poly(Lactic Acid) and Related Materials

Moshe Kol*

School of Chemistry, Tel Aviv University, Ramat AvivTel Aviv 69978, Israel


Poly(lactic acid) (PLA) is a biodegradable polymer derived from bio-renewable

resources having commodity-plastic and biomedical applications. PLA is synthesized by the catalyzed ring opening polymerization (ROP) of lactide. Traditionally employed homoleptic complexes such as tin octoate or aluminum isopropoxide catalyze the polymerization of rac-lactide to give stereo-irregular polymers, however, catalysts introduced in the last fisteen years that include metal complexes of polydentate ligands enabled the synthesis of stereoregular PLA from rac-lactide and from meso-lactide. In this presentation we will give some background on ring opening polymerization, and describe several literature examples of catalysts leading to stereoregular polymerization of lactide and related monomers.[1] We will also describe several recent examples from our own work.[2] [1] For several recent reviews, see: a) Dijkstra, P. J.; Du, H.; Feijen, J. Polym. Chem.

2011, 2, 520. b) Chisholm. M. H. Pure Appl. Chem. 2010, 82, 1647. c) Kiesewetter, M. K.; Shin, E. J.; Hedrick, J. L.; Waymouth, R. M. Macromolecules 2010, 43, 2093. d) Stanford, M. J.; Dove, A. P. Chem. Soc. Rev. 2010, 39, 486. e) Thomas, C. M. Chem. Soc. Rev. 2010, 39, 165. f) Platel, R. H.; Hodgson, L. M.; Williams, C. K. Polym. Rev. 2008, 48, 11.

[2] a) Sergeeva, E.; Kopilov, J.; Goldberg, I.; Kol, M. Inorg. Chem. 2010, 49, 3977. b) Stopper, A. L.; Okuda, J.; Kol, M. Macromolecules 2012, 45, 698.

Zinc Cluster Catalyzed Transesterification and Oxazoline Synthesis Kazushi Mashima*

Department of Chemistry, Graduate School of Engineering Science,

Osaka University, Toyonaka, Osaka 560-8531, Japan.


The ester moiety represents one of the most ubiquitous functional groups in organic

compounds, serving as both key intermediate and protecting group in organic transformations. Among various esterification reactions established so far, one of the most convenient synthetic methods is transesterification, in which methyl or ethyl esters react with various alcohols to give the corresponding esters in one step. Recently, we developed m-oxo-tetranuclear zinc cluster Zn4(OCOCF3)6O as an efficiently catalyst for transesterification, including chemoselective acylation of hydroxy group in the presence of aliphatic amino group, catalytic acetylation of alcohols and catalytic deacetylation of acetates. Because of mildness of the reaction conditions, these reactions have a high degree of functional-group tolerance.[1]-[3] The catalytic synthesis of oxazoline by treating esters and carboxylic acids with aminoalcohols is also delivered.

[1] Y. Maegawa, Y. Hayashi, T. Iwasaki, T. Ohshima, and K. Mashima, ACS Catalysis,

1, 1178-1182 (2011). [2] T. Iwasaki, K. Agura, Y. Maegawa, Y. Hayashi, T. Ohshima, and K. Mashima, Chem.

Eur. J., 16, 11567-11571 (2010). [3] T. Ohshima, T. Iwasaki, Y. Maegawa, A. Yoshiyama, and K. Mashima, J. Am. Chem.

Soc., 130, 2944-2945 (2008); Highlighted in Nature, 452, 415-416 (2008); Science, 319, 1163 (2008).

Salt-free Reduction of Tantalum and Tungsten Halides for Generating Low-valent Catalytically Active Species

Kazushi Mashima* Department of Chemistry, Graduate School of Engineering Science,

Osaka University, Toyonaka, Osaka 560-8531, Japan.


Low valent early transition metal complexes have been utilized as reagents and

catalysts for mediating bond formation reaction including olefin polymerization and oligomerization and olefin metathesis reaction. Various reducing reagents have been developed for reducing these metal halides; however, the complexation of the resulting salt with the desired low-valent species hampered their isolation and lowered their reactivity. Thus, we have developed a new methodology for generating salt-free low-valent species by treating metal halides with 3,6-bis(trimethylsilyl)-1,4-cyclohexadiene or its methyl derivative.[1],[2] The merit of this reduction is no salt formation but produces 2 equiv of Me3SiCl, C6H5R (R = H or CH3). The highlight of such methodology is that ligand-free Ta(III) species catalyzes the trimerization of ethylene to 1-hexene with >98% selectivity without any detection of internal olefins through a metallacycle mechanism.[2] In this lecture, a personal approach how to propose any idea is described. [1] H. Tsurugi, T. Saito, H. Tanahashi, J. Arnold, and K. Mashima, J. Am. Chem. Soc.,

133, 18673-18683 (2011). [2] R. Arteaga-Mueller, H. Tsurugi, T. Saito, M. Yanagawa, S. Oda, and K. Mashima, J.

Am. Chem. Soc., 131, 5370-5371 (2009).

Palladium- and Nickel-Catalyzed Cross-Coupling Reactions of Alkyl Electrophiles Gregory C. Fu*

Department of Chemistry, Massachusetts Institute of Technology, 77 Massachusetts Avenue, Room 18-290,

Cambridge, MA 02139-4307 USA


Despite the tremendous accomplishments that have been described in the

development of palladium- and nickel-catalyzed carbon–carbon bond-forming processes, it is nevertheless true that many significant opportunities remain. For example, to date the overwhelming majority of studies have focused on couplings between two sp2-hybridized reaction sites (e.g., an aryl metal with an aryl halide).

As of 2001, there were relatively few examples of palladium- or nickel-catalyzed coupling reactions of alkyl electrophiles. During the past several years, we have pursued the discovery of palladium- and nickel-based catalysts for coupling activated and unactivated primary and secondary alkyl electrophiles that bear β hydrogens. Our recent efforts to develop broadly applicable methods, including enantioselective processes, will be discussed.


Enantioselective Nucleophilic Catalysis Gregory C. Fu*

Department of Chemistry, Massachusetts Institute of Technology, 77 Massachusetts Avenue, Room 18-290, Cambridge, MA 02139-4307 USA


Nucleophiles such as 4-(dimethylamino)pyridine (DMAP) and tertiary phosphines

catalyze a wide array of useful and interesting reactions. We are pursuing the development of asymmetric processes catalyzed by enantiopure DMAP derivatives and phosphines.


Adding Aliphatic C-H Bond Oxidations to Synthesis M. Christina White*

Department of Chemistry, University of Illinois, 270 Roger Adams Laboratory, 600 South Mathews Ave., Urbana, IL 61801, USA

e-mail: [email protected] Aliphatic C-H oxidations have appeared in the literature sporadically over the past

century. However, synthetic chemists considered these transformations to be too poorly selective and/or reactive for routine utilization in synthesis. As recently as 2007, chemists considered bio-inspired catalysts with elaborate binding pockets to be the most promising candidates for achieving site-selectivity for intermolecular reactions with unactivated, aliphatic C-H bonds. Reactivity differences between these very inert bonds were thought to be too minor for a small molecule catalyst to discriminate effectively. Remarkably, only four years after this sentiment pervaded, it is now widely accepted that predictable selectivity and good reactivity for aliphatic C-H oxidations is possible with electrophilic small molecule catalysts and simple organic reagents.

mailto:%[email protected]

Three factors have that have been crucial to this paradigm shift in how the reactivity of C-H bonds is viewed will be discussed: first, the discovery of a selective Fe(PDP) catalyst that operates under synthetically useful conditions (limiting substrate) and reliably furnishes ≥ 50% isolated yields of mono-oxidized products; second, the systematic delineation of predictable “rules” for the selectivities observed that are generalizable to other electrophilic oxidants; and, third, the demonstration that these rules persist in diverse, complex molecule settings. Perhaps the most important finding with Fe(PDP) is that the same selectivity rules that govern the differential reactivity of traditional functional groups (i.e., electronics, sterics, and stereoelectronics) also govern the reactivity of relatively inert C-H bonds.

CH Oxida thesis tions and Organic SynM. Christina White*

Department of Chemistry, University of Illinois, 270 Roger Adams Laboratory, 600 South Mathews Ave., Urbana, IL 61801, USA

e-mail: t uwhi [email protected] Among the frontier challenges in chemistry in the 21st century are the

interconnected goals of increasing control of chemical reactivity and synthesizing stereochemically and functionally complex molecules with higher levels of efficiency. Although it has been well demonstrated that given ample time and resources, highly complex molecules can be synthesized in the laboratory, too often current reaction manifolds do not allow chemists to match the efficiency achieved in Nature.

mailto:%[email protected]

Traditional organic methods for installing oxidized functionality rely heavily on acid‐base reactions that require extensive functional group manipulations (FGMs) including wasteful protection‐deprotection sequences. Due to their ubiquity in complex molecules and inertness to most organic transformations, C‐H bonds have typically been ignored in the context of methods development for total synthesis. Discovery and development of highly selective oxidation methods for the direct installation of oxygen, nitrogen and carbon into allylic and aliphatic C‐H bonds of complex molecules and their intermediates are discussed. Unlike Nature which uses elaborate enzyme active sites, this chemistry harnesses the subtle electronic, steric, and stereoelectronic interactions between C‐H bonds and small molecule transition metal complexes to achieve high regio‐, chemo‐, and stereoselectivities. Our current understanding of these interactions gained through empirical and mechanistic studies will be discussed. Novel strategies for streamlining the process of complex molecule synthesis enabled by these methods will be presented. Collectively, our program aims to change the way that complex molecules are constructed by defining the principles that govern reactivity of C‐H bonds in complex molecule settings.

Poster Abstracts

Poster 1

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

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

Organisch-Chemisches Institut der Universität Heidelberg, Im Neuenheimer Feld 270, 69120 Heidelberg, Germany; c BASF 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.

Poster 2

The Total Synthesis of Spirastrellolide A Methyl Ester Alexander Arlt, Alois Fürstner*

Max-Planck-Institut für Kohlenforschung


Spirastrellolide A Methyl Ester was isolated in 2003 from the Carribean marine sponge

spirastrella coccinea as the first member of a family of macrolide natural products (Spirastrellolides A-G).[1] The Spirastrellolides consist of a 47 membered polyketide backbone and exhibit outstanding biological activity.

In 2008 Paterson et al. published the first total synthesis of Spirastrellolide A Methyl Ester followed shortly thereafter by the reports of our group on the total synthesis of Spirastrellolide F

Methyl Ester.[2] Due to the high convergency of our synthetic strategy small changes to the fragments extend it to the total synthesis of Spirastrellolide A, the initial target of our synthetic efforts. In our successful approach towards Spirastrellolide A a dithiane at the C16 position (a ketone equivalent) was used for fragment coupling. The corresponding ketone could then be transformed at a late stage into the C15-C16

double bond by an efficient two step sequence, giving the core of Spirastrellolide A. Direct attachment of the side chain via Julia-Kocienski olefination completed our Total Synthesis of

pirastrellolide A Methyl Ester.[3]

[2]al.

10.1002/anie.201108594. [3] A. Arlt, A. Fürstner, 2012, manuscript in preparation.

S [1] Andersen et al. JACS 2003, 125, 5296 and JOC 2007, 72, 9842.

a) Paterson et al. ACIE 2008, 47, 3016 and ACIE 2008, 47, 3021; b) Fürstner et al. ACIE 2009, 48, 9940 and ACIE 2009, 48, 9946; c) 2nd generation: Fürstner et ACIE 2011, 50, 8739; Paterson et al. ACIE 2012, DOI:

Poster 3

Auto-Tandem Catalysis with Ruthenium: Remote Hydroesterification of Olefins Nicolas Armanino, Erick M. Carreira*

Laboratorium für Organische Chemie, ETH Zürich, CH-8093 Zürich, Switzerland. e-mail: [email protected]

One-pot processes that involve cascading reactions provide attractive tools for

organic synthesis by simplifying operations and reducing the number of required intermediate isolations. Of particular interest are reactions that use a single catalytic entity capable of promoting multiple distinct steps without the need for operator intervention. In the course of our investigations, we have developed an auto-tandem catalytic system for the isomerization-hydroesterification sequence of internal olefins.

The system is based on low-valent ruthenium carbonyl clusters, enabling the

incorporation of a C1-unit by C-C bond formation onto a broad scope of allylic amines and alcohols. The process is characterized by operational simplicity, results in the functionalization of a remote position of the substrate and permits easy access to chiral lactone and lactam building blocks. Our mechanistic working model suggests that the key to success in this cascade is the formation of an active ruthenium cluster hydride by metal protonation, capable of promoting fast olefin isomerization that prevails over undesired decarbonylation pathways.

Poster 4

Highly Modular Synthesis of P-chiral NHCP Ligands for Rhodium-Catalyzed Asymmetric Hydrogenation

Marcel Brill, Patrick Hanno-Igels, Peter Hofmann*

Organisch-Chemisches Institut, Universität Heidelberg, INF 270, D-69120 Heidelberg, Germany


In spite of numerous highly efficient and selective catalysts that have been prepared

for rhodium-catalyzed asymmetric hydrogenation, the development of ligands which can be conveniently synthesized and easily modified continues to be an important issue in order to selectively hydrogenate a wide variety of substrates.[1] We have recently developed an efficient synthesis of sterically bulky and electron-rich N-phosphino-methyl functionalized N-heterocyclic carbenes that allows facile tuning of steric and electronic properties of the ligands.[2] Here, we present our new highly modular synthetic approach to P-chiral N-phosphinomethyl substituted NHCs of type 1 and our first results related to the synthesis of catalysts bearing ligands 1 and 2 and their performance in asymmetric hydrogenation.[3]

[1] a) Y. Chi, W. Tang, W. Zhang in Modern Rhodium-Catalyzed Organic Reactions (Ed.: P. A. Evans), Wiley-VCH, Weinheim, 2005, 1.

[2] a) U. Herrlich (neé Blumbach), Dissertation, Universität Heidelberg 2007; b) P. Hofmann, P. Hanno-Igels, O. Bondarev, C. Jäkel, WO 2009/10116 (A2).

[3] a) M. Brill, ongoing Dissertation, Universität Heidelberg; b) C. Jäkel, P. Hofmann, C. Scriban, P. Hanno-Igels, WO 2011/012687 (A1).

Poster 5

New Concepts for Ruthenium-Catalyzed Olefin Metathesis Reactions José Cabrera,a Robin Padilla,a Kristina Wilckens,a Peter Hofmann,*a,b Michael

Limbach*a,c

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

69120 Heidelberg, Germany; cBASF SE, Synthesis and Homogeneous Catalysis, GCS/C, M313, Carl Bosch Straße 38, 67056 Ludwigshafen, Germany

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

Homogenous catalysts capable of strongly binding to a solid support in active form and without the need for extensive synthetic manipulations of the catalyst or support, are attractive from an industrial perspective. Building on previous work with high silica affinity Ru-complexes[1] and subsequent high-throughput studies,[2] we developed and studied a new class of heterogeneous catalysts consisting of NHC-modified Ru-complexes adsorbed on to silica. The Ru complexes were immobilized via a simple solvent transfer procedure and tested in a variety of olefin metathesis reactions under continuous flow conditions. These new complexes exhibited substantially higher activities compared to Re2O7, a classical, state of the art heterogeneous metathesis catalyst.

While ruthenium complexes with phosphorus-based ligands in the trans geometry are the most commonly encountered, previous work has shown that chelating cis bisphosphane ligands used with cationic ruthenium complexes exhibit significantly enhanced catalytic activity in ROMP reactions.[3] As such, another area of study is focused on the synthesis of Ru-carbene complexes incorporating new, chelating cis phosphinomethyl substituted NHC ligands for use in ROMP reactions.

[1] J. A. Schachner, J. Cabrera, R. Padilla, C. Fischer, P. A. van der Schaaf, R. Pretot, F.

Rominger, M. Limbach, ACS Catal. 2011, 1, 872-876. [2] J. Cabrera, R. Padilla, R. Dehn, S. Deuerlein, Ł. Gułajski, E. Chomiszczak, J. H.

Teles, M. Limbach, K. Grela, Adv. Synth. Catal. 2012, in press. [3] S. M. Hansen, M. A. O. Volland, F. Rominger, F. Eisentrager, P. Hofmann, Angew.

Chem. Int. Ed. 1999, 38, 1273-1276.

Poster 6

The Synthesis of a New Class of Chiral Pincer Ligands and Their Applications in Enantioselective Catalysis

Qing-Hai Deng, Hubert Wadepohl, Lutz H. Gade*

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

Germany


A new class of chiral tridentate N-donor pincer ligands, bis(oxazolinyl-

methylidene)isoindolines (boxmi) has been synthesized in three steps starting from readily available phthalimides.1

These ligands were subsequently applied in the Ni-catalyzed enantioselective

fluorinations and the Cr-catalyzed enantioselective Nozaki- Hiyama-Kishi reaction to obtain the corresponding products with high enantioselectivities.[1] Recently, we reported the Cu-catalyzed enantioselective alkylation of β-ketoesters using alcohols for the in situ preparation of alkylating reagents.[2] The alkylation products derived from 2-substituted allylic alcohols or their corresponding iodides were subsequently converted to spirolactones, bi-spirolactones and related chiral target products. [1] Deng, Q.-H.; Wadepohl, H.; Gade, L. H. Chem. Eur. J. 2011,17, 14922. [2] Deng, Q.-H.; Wadepohl, H.; Gade, L. H. J. Am. Chem. Soc. 2012, DOI:

10.1021/ja211859w.

Poster 7

The Role of Metal-Hydroxide Complexes in Late-Transition Metal Mediated Transmetalation Reaction: The Case of Gold

Stéphanie Dupuy, Luke Crawford, Michael Buhl, Alexandra M. Slawin, Steven P. Nolan*

EASTCHEM School of Chemistry, University of St Andrews, St Andrews, KY16 9ST, UK


Metal-catalyzed cross-coupling reactions are commonly employed as a powerful

synthetic tool for the formation of C-C bonds and among them the Suzuki-Miyaura reaction plays a prominent role.[1] A key step in this reaction features the transmetalation of a boron reagent to palladium. Although, this step has been extensively studied, the actual reaction sequence involved is still a matter of debate.[2] Very recent results reported by Hartwig[3] and Amatore and Jutand[4] support a hypothesis where the transmetalation reaction involves a palladium hydroxide reacting with the boronic acid. In our search for new reactions with (NHC)-gold(I) complexes, we have developed an improved synthetic protocol for the transmetalation reaction between arylboronic acids on [Au(NHC)]-type complexes and have recently examined whether the intriguing observation of the intermediacy of a metal-hydroxide complex might also exist in d10 systems.[5]

[1] N. Miyaura, A. Suzuki, Chem. Rev. 1995, 95, 2457-2483. [2] M.-E. Moret, D. Serra, A. Bach, P. Chen, Angew. Chem. Int. Ed. 2010, 49,

2873-2877. [3] J. F. Hartwig, B. P. Carrow, J. Am. Chem. Soc. 2011, 133, 2116-2119. [4] C. Amatore, A. Jutand, G. Le Duc, Chem. Eur. J. 2011, 17, 2492-2503. [5] Manuscript submitted.

Poster 8

PNS-type Ruthenium Pincer Complexes Moti Gargir,a Gregory Leitus,b Linda J.W. Shimon,b Yehoshua Ben-David,a David

Milsteinb*

aDepartment of Organic Chemistry, bDepartment of Chemical Research Support, Weizmann Institute of

Science, Rehovot 76100, Israel


Dearomatized pincer complexes (PNN)Ru(H)CO 1 and (PNP)Ru(H)CO 2, which

were reported by our group catalyze several “green” catalytic reactions. 1 is an efficient catalyst for the dehydrogenative coupling of alcohols to esters, acylation of secondary alcohols by esters with dihydrogen liberation, direct dehydrogenative coupling of alcohols and amines to form amides.[ 1 ] Unlike 1, complex 2 catalyzes the dehydrogenative coupling of alcohols and amines to generate imines, rather than amides.[2] Apparently, modification of the pincer “arm” has a profound effect on catalytic activity. The thioether “arm” of PNS complexes is expected to be hemilabile[3]-[5] but, unlike the PNN ligand, it lacks the ability to serve as a base. Here we present new pincer ruthenium complexes based on a new PNS ligand, including their synthesis, reactivity and catalytic activity. [1] Gunanathan, C.; Milstein, D. Accounts Chem. Res. 2011, 44, 588-602. [2] Milstein, D.; Gnanaprakasam, B.; Zhang, J. Angew. Chem. Int. Edit. 2010, 49,

1468-1471. [3] Vinas, C.; Angles, P.; Sanchez, G.; Lucena, N.; Teixidor, F.; Escriche, L.; Casabo, J.;

Piniella, J.; Alvarez- Larena, A.; Kivekas, R.; Sillanpaa, R. Inorg. Chem. 1998, 37 701-707.

[4] Canovese, L.; Visentin, F.; Chessa, G.; Uguagliati, P.; Santo, C.; Bandoli, G.; Maini, L. Organometallics 2003, 22, 3230-3238.

[5] Bassetti, M.; Capone, A.; Salamone, M. Organometallics 2004, 23, 247-252.

Poster 9

Diastereoselective Synthesis of Tricyclic Indolizine Alkaloids Using En-Yne-En-RRM RCM Cascade

Matthias T. Grabowski, Siegfried Blechert*

TU Berlin – Berlin Institute of Technology, Institute of Chemistry, Str. des 17. Juni 115, D-10623 Berlin


Ring-rearrangement metathesis has proven to be a powerful synthetic tool for the

construction of carbo- and heterocycles and has been efficiently applied to various natural product syntheses of diverse polycyclic systems. A cascade reaction with a diastereoselective En-Yne-En-RRM RCM as a key step has been developed for the synthesis of tricyclic indolizines.

N

[Ru]

R

N

R

N

R

d-RRM RCM

H

X[Ru]HX

R

HX: p-TsOH, TfOH,HBF4 or etc.

Dienynes turned out to be challenging substrates for tandem metathesis processes,

due to a lack of selectivity-controlling groups. A rational design for the desired pathway is shown within this work: a cyclic ene subunit with a triple bond in an appropriated distance for a favored RRM, and a R-group which is not diminishing the catalyst activity, for the post-RRM RCM, offer perfect reaction control and avoid undesired side pathways.

This attractive and protecting-group-free route can be easily used for the synthesis of lepadiformine/ cylindricine or other izidine alkaloids.

Poster 10

Theoretical Investigations on an Iron Catalyzed Alkylation Reaction Berit Heggen, G. Gopakumar, Walter Thiel*

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

45470 Mülheim an der Ruhr, Germany


Cross-coupling reactions are well-established in synthetic chemistry. But one major

drawback is the use of expensive, e.g. palladium, catalysts. Therefore, iron got into focus as a cheap and benign metal to assist cross-coupling reactions.[1] Organolithium compounds in conjunction with iron halides proved to be suitable. However, the mechanistic details and nature of possible reaction intermediates are yet to be confirmed.[2] In this regard, the recent synthesis and structural characterization of an organoferrate complex 1 by Fürstner and co-workers, has opened up new directions.[3]

Two possible mechanistic pathways have been proposed for alkylation reactions by

the use of 1: a substitution mechanism and a "classical" oxidative addition/reductive elimination pathway. In this context, we have applied Density Functional Theory (DFT) methodologies to gain further insights.

[1] Sherry, B. D.; Fürstner, A. Acc. Chem. Res. 2008, 41, 1500. [2] Kauffmann, T, Angew. Chem. Int. Ed. 1996, 35, 386-403. [3] Fürstner, A.; Martin, R.; Krause, H.; Seidel, G.; Goddard, R.; Lehmann, C. W. J.

Am. Chem. Soc. 2008, 130, 8773-8787.

Poster 11

N-Heterocyclic Carbene Complexes and their Catalytic Activity Christoph Hubbert, A. Stephen K. Hashmi*

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

Im Neunheimer Feld 270, D-69124 Heidelberg, Germany


N-heterocyclic carbene complexes of different metals are well established catalysts

for several reactions in academic and industrial laboratories.[1],[2] A typical synthesis of such complexes is often a multi-step procedure via an imidazolium salt and a transmetallation step. Hence, a short and efficient route towards high active catalysts would be very useful.

On my poster I present an easy route towards N-heterocyclic carbene complexes

starting from easily accessible metal isocyanide complexes of several transition metals.[3]

Furthermore, the results of catalytic test reactions which show the exceptional activity of the catalyst, will be presented. [1] Cazin, C.S.J., N-Heterocyclic Carbenes in Transition Metal Catalysis and

Organocatalysis, Heidelberg, London, New York: Springer 2011. [2] Nolan, S.P., N-Heterocyclic Carbenes in Synthesis, Weinheim: Wiley-VCH 2006. [3] Hashmi, A.S.K.; Lothschütz, C.; Böhling, C.; Hengst, T.; Hubbert, C.; Rominger, F.

Adv. Synth. Catal. 2010, 352, 3001–3012.

Poster 12

Triflic Acid Catalyzed Diacetoxylation of Alkenes Yan-Biao Kanga, Lutz H. Gade*a,b

a Catalysis Research Laboratory (CaRLa), Im Neuenheimer Feld 584, 69120 Heidelberg, Germany b Anorganisch-Chemisches Institut, Universität Heidelberg, Im Neuenheimer Feld 270, 69120 Heidelberg,

Germany


Clean and efficient diacetoxylation reactions of alkenes catalyzed by triflic acid

using commercially available (Diacetoxyiodo)benzene or peroxyacids as oxidants were presented.[1],[2] Mechanisms based on experimental evidence were also described.

[1] Kang, Y.-B.; Gade, L. H. J. Am. Chem. Soc. 2011, 133, 3658.

[2] Kang, Y.-B.; Gade, L. H. J. Org. Chem. 2012, 77, 1610.

Poster 13

Stereocontrolled Ring-Opening-Polymerization of Lactide Monomers by Bis(phenolato) Rare-Earth Metal Initiators

Andreas Kapelskia, Jean-Charles Buffetb, Jun Okudaa* aInstitut für Anorganische Chemie, RWTH Aachen University, Landoltweg 1, 52074 Aachen, bChemistry

Research Laboratory, Mansfield Road, Oxford, OX1 3TA (UK) e-mail: [email protected]

Monomeric rare-earth metal bis(dimethylsilylamido) complexes bearing an (OSSO)-

type chelating bis(phenolato) ligand [(OSSO)Ln{N(SiMe2H)2}(THF)] (Ln = Sc, Y) were isolated from amine elimination reaction by rare-earth metal tris{bis(dimethylsilylamido)} precursors [Ln{N(SiMe2H)2}3(THF)x] (Ln = Sc, x = 1; Ln = Y, x = 2) with one equivalent of tetradentate (OSSO)-type bis(phenol).

Scheme 1: Synthesis of rare-earth metal bis(dimethylsilylamido) complexes. These rare-earth metal initiators polymerize rac-lactide to heterotactic polylactide

(PLA) and meso-lactide to highly syndiotactic PLA. The variation of the bridge (flexible or rigid, chiral or achiral) has been studied to their influence on the level of tacticity of the meso- or rac-polylactides.

[1] J.-C. Buffet, A. Kapelski, J. Okuda, Macromolecules 2010, 43, 10201 – 10203. [2] A. Kapelski. J.-C. Buffet, T. P. Spaniol, J. Okuda, Chem. Asian J., DOI:

10.1002/asia.201100826.


Poster 14

Mechanochemical Degradation of Lignin Model Compounds T. Kleine, J. Buendia, J. Mottweiler, E. Zuidema, C. Bolm*

Institute of Organic Chemistry, Landoltweg 1, D-52056 Aachen, Germany

e-mail: [email protected]–Aachen.de; [email protected]–Aachen.de

Lignin is a potentially cheap and substantial source for platform chemicals or

combustion engine fuel additives[1] although its exploitation suffers from high technical barriers.[ 2 ] Poor solubility and structural diversity of lignin are the most critical obstacles for chemical conversion.[3],[4] In respect to this challenging, highly complex substrate, advanced reaction techniques such as ball milling are expedient.[5]

We now present a protocol which allows the efficient and selective cleavage of β-O-4-linkage model compounds[6] by use of cheap bulk reagents under organocatalytic conditions and without solvent, inert gas atmosphere or external sources of heat in the ball mill. The model compounds, which are accessible in a three step synthesis, are treated with sodium hydroxide in the presence of DMAP in the ball mill to give phenolic and acetophenone derived degradation products in good yield. [1] J. C. Hicks, J. Phys. Chem. Lett. 2011, 2, 2280 – 2287. [2] J. Zakzeski, P. C. Bruijnincx, A. L. Jongerius, B. M. Weckhuysen, Chem. Rev. 2010,

110, 3552 – 3599. [3] M. Lawoko, A. R. P. van Heiningen, J. Wood Chem. Tech. 2011, 31, 183 – 203. [4] D. Takada, K. Ehara, S. Saka, J. Wood Sci. 2004, 50, 253 – 259. [5] S. L. James, C.J. Adams, C. Bolm, D. Braga, P. Collier, T. Friščić, F. Grepioni, K. D.

M. Harris, G. Hyett, W. Jones, A. Krebs, J. Mack, L. Maini, A. G. Orpen, I. P. Parkin, W. C. Shearouse, J. W. Steed, D. C. Waddell, Chem. Soc. Rev. 2012, 41, 413 – 447.

[6] J. Buendia, J. Mottweiler, C. Bolm, Chem. Eur. J. 2011, 17, 13877 – 13882.

Poster 15

Palladium-Catalyzed Cross-Coupling Reactions and Direct C–H Bond Functionalizations

Christoph Kornhaaß, Lutz Ackermann* Institut für Organische und Biomolekulare Chemie, Georg-August-Universität Göttingen, Tammanstr. 2,

37077 Göttingen, Germany


Heteroatom-substituted secondary phosphine oxides (HASPO) have emerged as

efficient preligands for transition metal-catalyzed cross-coupling reactions.[1],[2] Recently, we synthesized well-defined air-stable palladium complexes derived from (HA)SPO-preligands, which turned out to be versatile catalysts for efficient Kumada-Corriu cross-coupling reactions of unactivated (hetero)aryl- and alkenyl tosylates with an improved catalytic activity as compared to the corresponding in-situ generated catalysts.[3]

Moreover, these complexes were found to be highly active catalysts in

environmentally benign direct C–H Bond functionalizations of various azoles.[4],[5]

[1] L. Ackermann, Synlett 2007, 507–526. [2] L. Ackermann, Isr. J. Chem. 2010, 50, 652–663. [3] a) L. Ackermann, A. Althammer, Org. Lett. 2006, 8, 3457–3460; b) L. Ackermann,

H. K. Potukuchi, A. R. Kapdi, C. Schulzke, Chem. Eur. J. 2010, 16, 3300–3303. [4] L. Ackermann, A. R. Kapdi, S. Fenner, C. Kornhaaß, C. Schulzke, Chem. Eur. J.

2011, 17, 2965–2971. [5] L. Ackermann, S. Barfüßer, C. Kornhaaß, A. R. Kapdi, Org. Lett. 2011, 13,

3082–3085.

Poster 16

Investigation of Fundamental Steps in the Formation of Acrylates from CO2 and Ethylene

Michael Lejkowski,a Ronald Lindner,a Takeharu Kageyama,a Philipp-Nikolaus Plessow,a Stephan Schunk,b Michael Limbacha,c*

aCaRLa - Catalysis Research Laboratory, Im Neuenheimer Feld 584, D-69120 Heidelberg, Germany; bhte

Aktiengesellschaft, Kurpfalzring 104, D-69123 Heidelberg, Germany; cBASF SE, Synthesis and

Homogeneous Catalysis, GCS/C – M313, Carl-Bosch-Strasse 38, D-67056 Ludwigshafen, Germany


Sodium acrylate is the main component of common superabsorbents. Its direct

synthesis via oxidative coupling of CO2 and ethylene would offer an interesting alternative to the industrial process currently utilized. Nickelalactones (1), reported in the revolutionary works of Hoberg,[1] were frequently discussed as possible intermediates in a hypothetic catalytic synthesis of acrylic acid[2] and its derivatives (Figure 1). In order to develop a process for catalytic formation of acrylates from CO2 and ethylene a wide spectrum of ligands and additives is currently investigated, with both experimental and quantum chemical methods.

ONa

O

LnNi0

NiLnO

O

NiLnO

O

H

oxidativecoupling

ligandexchange

β-hydrideelimination

reductiveelimination

CO2 +

NaOH

ONa

O

LnNi0 1

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

[2] Fischer, R.; Langer, J.; Malassa, A.; Walther, D.; Görls, H.; Vaughan, G. Chem. Commun. 2006, 23, 2510-2512.

Poster 17

Ring opening polymerization of Propyleneoxid by N-Heterocyclic Carbene Precursor

Ronald Lindner,a Michael Lejkowski,a Peter Deglmann,b Kerstin Wiss,c Michael Limbacha,d*

aCaRLa − Catalysis Research Laboratory, Im Neuenheimer Feld 584, 69120 Heidelberg, Germany, bBASF SE, GMC/M – B1, 67056 Ludwigshafen, Germany, cBASF SE, GMU/A – B1, 67056

Ludwigshafen, Germany, dBASF SE, GCS/C – M313, 67056 Ludwigshafen, Germany


Over the last decade NHC catalysts for the ROP of cyclic esters gathered

considerable attention.[ 1 ] However, the application of NHCs for the ring-opening polymerization of epoxides is significantly less investigated.[2] Within this work we demonstrate the application of N-heterocyclic carbenes adducts with CO2 (NHC-CO2) for the ring-opening polymerization of propyleneoxide (PO) under industrially relevant conditions.

NHC-precursor:NN R2R1

CO2

NHC

RO

+R

OOH

n

ΔT − CO2

cat.:

OH

A further objective of this work was the investigation of the structure-activity relationship of the NHC scaffold. Additional new insights in the mechanism of this reaction were obtained. [1] a) Kamber, N. E.; Jeong, W.; Waymouth, R. M. Chem. Rev. 2007, 107, 5813–5840.

b) Kiesewetter, M. K.; Shin, E. J.; Hedrick, J. L.; Waymouth, R. M. Macromolecules 2010, 43, 2093–2107.

[2] a) Raynaud, J.; Ottou, W. N.; Gnanou, Y.; Taton, D. Chem. Commun. 2010, 46, 3203–3205. b) Raynaud, J.; Absalon, C.; Gnanou, Y.; Taton, D. Macromolecules 2010, 43, 2814–2823. c) Raynaud, J.; Absalon, C.; Gnanou, Y.; Taton, D. J. Am. Chem. Soc. 2009, 131, 3201–3209.

Poster 18

The Roles of Au-F and Au-Au Interactions in Homogeneous Gold Catalysis Neal P. Mankad, F. Dean Toste*

University of California at Berkeley


Traditionally, homogeneous Au catalysis has consisted predominantly of

redox-neutral, Lewis acidic mechanisms. Recently, however, a new generation of Au-catalyzed two-electron redox cycles allowing for cross-coupling transformations has been discovered. These reactions often utilize the electrophilic fluorinating agent, Selectfluor, as a sacrificial oxidant, indicating a special role for gold(III) fluoride intermediates in these processes. Additionally, a significant dependence of catalytic efficiency on Au-Au distance has been reported in several cases, indicating a special role for gold-gold interactions during catalysis. In order to gain insight into these phenomena, reactivity studies and physical measurements have been carried out on rare examples of gold(III) fluoride complexes as well as several complexes with Au-Au interactions. On the basis of these studies, conclusions on the important roles of Au-F and Au-Au interactions in Au-catalyzed two-electron redox cycles will be presented. Based on these studies, a new generation of catalysts has been designed that allows for more efficient catalysis and careful mechanistic analysis. Preliminary results with these new catalysts also will be presented.

Poster 19

Selective and Multiple Functionalization of N-Heterocycles and Benzylic Cross-Coupling of Quinolines via Mg- and Zn-Organometallic Intermediates

Sophia M. Manolikakes, Milica Jaric, Andreas K. Steib, Stéphanie Duez, Paul Knochel*

Ludwig-Maximilians-Universität München, Department Chemie, Butenandtstr. 5-13, Haus F, 81377

München, Germany


Recently our group has demonstrated that the metalation of pyridine and quinoline

can be achieved by the use TMPMgCl·LiCl (TMP = 2,2,6,6-tetramethylpiperidyl) in the presence of the lewis acid BF3·OEt2.[1] This metalation protocol can also be applied to more complex N-heterocycles such as quinine and nicotine. The resulting Mg-compounds react with various electrophiles and also undergo transition metal-catalyzed cross-coupling reactions.[2] In the case of quinine the procedure can be modified in such a way, that it is possible to switch from position 3 of the quinoline scaffold to position 2. Besides TMPMgCl·LiCl, the milder base TMP2Zn·MgCl2·2LiCl[3] may be applied for a successive metalation of the pyridine scaffold allowing a full ring functionalization. The even more sensitive base TMPZnCl·LiCl[ 4 ] allows to perform a benzylic metalation of methyl substituted quinolines and isoquinolines. Subsequent Pd(OAc)2- catalyzed arylation, in the presence of an adequate Phos-ligand, proceeds well with various aryl bromides. [1] Jaric, M.; Haag, B.A.; Unsinn, A; Karaghiosoff, K.; Knochel, P. Angew. Chem. Int

Ed. 2010, 49, 5454-5455. [2] Jaric, M.; Haag, B.A.; Manolikakes, S.M.; Knochel, P. Org. Lett. 2011, 13,

2309-2309. [3] Wunderlich, S.H.; Knochel, P. Angew. Chem. Int Ed. 2007, 46, 7685-7688. [4] Mosrin, M.; Knochel, P. Org. Lett. 2009, 11, 1837-1840.


Poster 20

Easy access to saturated abnormal NHC-gold(I) complexes 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


N-Heterocyclic carbenes (NHCs) are now one of the most popular class of ligands in

organometallic chemistry. This probably is based on the high reactivity and exceptional stability of the corresponding catalysts.[1] However, NHCs usually bind metals through the C2 position of the heterocycle, and the rare cases of abnormal binding (i.e., through C4 or C5) usually involve blocking the C2 position. After reporting the synthesis of NHC complexes from gold coordinated isonitrile compounds,[2] we report here the straightforward synthesis of saturated abnormal carbene gold (I) complexes. The synthesis is based on a [3+2] cycloaddition of azomethine ylides and isonitrile gold (I) complexes, and tolerates a wide variety of substituents on the nitrogen atoms, including aliphatic, aromatic and heteroaromatic groups. X-ray diffraction analysis unambiguously confirms the first saturated abnormal carbene structure.

[1] a) Köcher, C. K.; Hermann, W. A. Angew. Chem. Int. Ed. 1997, 36, 2162-2187; b)

Hahn, F. E.; Jahnke, M. C. Angew. Chem. Int. Ed. 2008, 47, 3122-3172. [2] a) Hashmi, A. S. K.; Lothschütz, C.; Böhling, C.; Hengst, T.; Hubbert, C.;

Rominger, F. Adv. Synth. Catal. 2010, 352, 3001-3012; b) A. S. K. Hashmi, C. Lothschütz, K. Graf, T. Häffner, A. Schuster, F. Rominger Adv. Synth. Catal. 2011, 353, 1407–1412

Poster 21

Diamination of internal alkenes Martínez Claudio,a Muñiz Kiliana,b*

aInstitute of Chemical Research of Catalonia (ICIQ), Spain; bCatalan Institution for Research and

Advanced Studies (ICREA), Spain


We have recently been interested in the application of palladium catalysts to realise

unprecedented diamination reactions of internal alkenes.[1]-[3] Within this context, the application of suitable high oxidation state palladium catalysis represents the key methodology. We now report the first protocol for palladium catalysed intermolecular diamination reactions of internal alkenes, which employ readily available nitrogen sources. The diamination products are formed with complete regioselectivity and chemoselectivity.[4]

NTos2Palladium-Catalyst

Iodo(III)Oxidant

HNO

HNTos2

Intermolecular diamination of internal alkenes:

Diamination Product

R

O

N OO

R

[1] Muñiz, K.; Hövelmann, C. H.; Streuff, J. J. Am. Chem. Soc. 2008, 130, 763. [2] Streuff, J.; Hövelmann, C. H.; Nieger, M.; Muñiz, K. J. Am. Chem. Soc. 2005, 125,

14586. [3] Muñiz, K. J. Am. Chem. Soc. 2007, 129, 14542. [4] Martínez, C.; Muñiz, K. manuscript in preparation.


Poster 22

Dioxocin nitrogen derivates: novel ligands for dinuclear complexes Martínez-Ferraté Oriol,a Josep Maria López-Valbuena,a George J. P. Britovsek,b*

Carmen Claver,c* Piet W. N. M. van Leeuwena*

aInstitute of Chemical Research of Catalonia (ICIQ), bDepartment of Chemistry, Imperial College London, cDepartament de Química Física i Inorgànica, Universitat Rovira i Virgili


Diiron centers are the active site for some enzymes such as hemerythrin, methane

monooxygenase, flavo-diiron proteins etc.[ 1 ] Dioxocin phosphorus derivates demonstrated their ability to form rhodium dinuclear complexes.[ 2 ] The nitrogen derivatives were developed in view of the advantages of nitrogen ligands, namely their chemical robustness, their stabilization of high oxidation state transition-metal species, and their affinity towards metals from the first period such as Fe and Cu.

In this communication we present the synthesis of dioxocin tetranitrogen derivatives. The bromodioxocin was aminated via an Ullman coupling reaction with ammonia. Further condensations with different pyridinocarboxaldehydes led to the formation of the new ligands. Dinuclear Fe complexes were formed with the use of these ligands. Several catalytic reactions are being studied. such as epoxidation and phenol coupling. [1] a) Wallar, B. J.; Lipscomb, J. D. Chem. Rer. 1996, 96, 2625-2657; b) Solomon, E.

I.; Brunold, T. C.; Davis, M. I.; Kemsley, J. N.; Lee, S.-K.; Lehnert, N.; Neese, F.; Skulan, A. J.; Yang, Y.-S.; Zhou, J. Chem. Rev. 2000, 100, 235-349. c) Friedle, S.; Reisner, E.; Lippard, S. J.; Chem. Soc. Rev., 2010, 39, 2768–2779

[2] López-Valbuena, J. M.; Escudero-Adan, E. C.; Benet-Buchholz, J.; Freixa, Z.; van Leeuwen, P. W. N M. Dalton Trans. 2010, 39, 8560-8574

Poster 23

Synthesis of Phospholes by 1,1-Carboboration Reaction Juri Möbus, Roland Fröhlich, Gerald Kehr, Gerhard Erker*

Organisch-chemisches Institut, WWU Münster, Corrensstraße 40, 48149 Münster


Bis(alkynyl)phosphanes were found to undergo clean reaction with B(C6F5)3 to yield

highly substituted 3-boryl-phospholes at reaction temperatures between 50 °C and 80 °C within hours. The boryl moiety was shown to undergo Suzuki-Miyaura-type cross coupling reactions with different aryl halides to form the 3-aryl phospholes in up to 77% yield.[1]

P

R

RC6F5

B(C6F5)2Ar

(Pd0)base

P

R

RC6F5

PhAr

B(C6F5)3 Ph-IPAr

R

R

Ar = Tipp, MesR = TMS, nPr, Ph

The mechanism of the transformation involves a sequence of two 1,1-carboboration reactions. The reactions proceed by migration of the phosphanyl substituent via the formation of a zwitterionic phosphirenium borate species.

[1] Möbus, J.; Bonnin, Q.; Ueda K.; Fröhlich R.; Itami K; Kehr G.; Erker G. Angew.

Chem. Int. Ed. 2012, 53, DOI: 10.1002/anie.201107398.

Poster 24

Metal-Driven Preorganization in Organocatalysis Tathagata Mukherjee, John A.Gladysz*

Texas A&M University, College Station, TX, USA


The concept of preorganization involves engineering a receptor to be complementary

to a guest prior to a binding event. This can render the host-guest interaction entropically and enthalpically more favorable. This notion can be extended further to chiral hydrogen bond donors as they are immensely popular in enantioselective organocatalysis.

NO2+

COOEt

COOEt 10 mol% catalystCH2Cl2, rt

4 days

COOEtEtOOC

NO2

93%, 96% (ee) 54%, 55% (ee)catalyst: RuGBI GBI

N

NH

NH

NHRuNH NOC

PF6

RuGBI

N

NH

NH

HNNH N

GBI

To put to test the effect of "metal-driven preorganization in organocatalysis" we have

chosen a 2-guanidinobenzimidazole derivative (GBI) as a simple hydrogen bond donor. GBI is an effective ligand, and upon complexation to transition or main group metals it becomes preorganized for several hydrogen bonding motifs as rotational degrees of freedom that are intrinsic to the ligand are greatly reduced. Upon preorganization both the reactivity and enantioselectivity are enhanced significantly.

Poster 25

Pd-Catalyzed C–H Arylation and Alkylation Using Radicals Generated Under Mild Conditions

Sharon R. Neufeldt, Dipannita Kalyani, Kate B. McMurtrey, Melanie S. Sanford*

University of Michigan, Ann Arbor, MI, USA


Palladium catalysis has been widely successful as a means to convert C-H bonds to

C–C bonds. Nevertheless, functionalization of unactivated C-H sites typically requires high temperatures, which can render these systems prohibitively harsh. Previous mechanistic studies on Pd-catalyzed C-H arylations from our group have suggested that the use of more kinetically reactive oxidants could permit lower reaction temperatures.[1] We reasoned that carbon-centered radicals, generated under mild conditions, might be more kinetically reactive alternatives to other common arylating oxidants. To this end, we have developed a room-temperature Pd-catalyzed C-H arylation that utilizes carbon radicals generated from aryldiazonium salts by visible-light photoredox catalysis.[2] We have further discovered that diaryliodonium salts, which are known to effect Pd-catalyzed C–H arylation under thermal conditions (100 ºC), can also operate under a Pd/photoredox manifold at room temperature. In addition, we are investigating the use of organoboron compounds as precursors to carbon-centered radicals for Pd-catalyzed C-H arylation and alkylation reactions. [1] Deprez, N. R.; Sanford, M. S. J. Am. Chem. Soc. 2009, 131, 11234–11241. [2] Kalyani, D.; McMurtrey, K. B.; Neufeldt, S. R.; Sanford, M. S. J. Am. Chem. Soc.

2011, 133, 18566–18569.

Poster 26

Limits of Activity: Weakly Coordinating Ligands in Arylphosphinesulfonato Pd(II) Polymerization Catalysts

Boris Neuwald, Franz Ölscher, Ingo Göttker-Schnetmann, Stefan Mecking*

Chair of Chemical Materials Science, Department of Chemistry, University of Konstanz, Germany


Catalytic insertion polymerization of ethylene and propylene is employed on a vast

scale. By contrast, an insertion polymerization of electron deficient polar substituted vinyl monomers has remained elusive. Phosphinesulfonato Pd(II)–complexes [(PÔ)PdMe(L)] are versatile precursors for the copolymerization of ethylene with polar monomers towards linear polymers and the past years have witnessed a remarkable advance of the scope of monomers amenable to insertion copolymerization.[1] The reactivity of well-defined single-component catalyst precursors [(PÔ)PdMe(L)] (1-L) towards acrylates depends crucially on the coordination strength of the ligand L. Highly reactive precursors with L = dmso for the first time enabled consecutive insertions to high-acrylate content ethylene copolymers, as well as homooligomerization of acrylates.[2] Detailed studies on the influence of the ligand L revealed that the (PÔ)PdMe fragment exhibits an intrinsic limitation with respect to coordination of weak donors, due to bridging coordination of the (PÔ)-ligand. The in situ generated ligand L free species 1 has been identified in homo- and copolymerization experiments as the most active possible catalyst. [1] a) Drent, E.; v. Dijk, R.; v. Ginkel, R.; v. Oort, B.; Pugh, R. I. Chem. Commun. 2002,

744-745; b) Nakamura, A; Ito, S.; Nozaki, K. Chem. Rev. 2009, 109, 5215-5244. [2] Guironnet, D.; Roesle, P.; Rünzi, T.; Göttker-Schnetmann, I;. Mecking, S. J. Am.

Chem. Soc. 2009, 131, 422-423.

Poster 27

Gold(I)-Catalyzed [2+2+2] Cycloaddition of Alkynes with Ketoalkenes Carla Obradors, Antonio M. Echavarren *

Institute of Chemical Research of Catalonia (ICIQ)

[email protected]

Gold has emerged as an exceptional catalyst for a variety of complex organic

transformations through the selective activation of alkynes, allenes and alkenes.[1] An interesting example that leads to elaborated molecular skeletons involves the cycloisomerization of enynes bearing a carbonyl group at the alkenyl chain.[2] We have now developed a new intermolecular version of this reaction for the synthesis of [3.2.1]-oxabicycles from alkynes and ketoalkenes using gold(I) complexes bearing bulky 1,1´-biphenyl-2-dialkylphoshines as catalysts.

O

O

O

O A (3 mol%)CH2Cl2

Ar

Me

O

Me

ArO

Me

Me

+DCE, 0.5 M, 80 ºC

C (3 mol%)

(5:1)

Ar +LAu+ (3 mol%)DCE, 50 ºCR3

O

R2R1

R1Ar

R3

R2

R1

R1 OiPr

iPr

iPr

PtBu

tBu

L=

15 examples42-99%

The scope of this process as well as theoretical studies to determine the reaction

mechanism will be presented. [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] Jiménez-Núñez, E.; Claverie, C. K.; Nieto-Oberhuber, C.; Echavarren, A. M. Angew. Chem. Int. Ed. 2006, 45, 5452. Huguet, N.; Echavarren, A. M. Synlett 2012, 23, 49. Schelwies, M.; Dempwolff, A. L.; Rominger, F.; Helmchen, G. Angew. Chem. Int. Ed. 2007, 46, 5598.

Poster 28

Hydroamination of Ethylene Catalyzed by Novel Platinum(II) N-Heterocyclic Carbene Complexes

José Cabrera,a Robin Padilla,a Michael Limbacha,b* aCatalysis Research Laboratory (CaRLa) – Im Neuenheimer Feld 584, 69120 Heidelberg, Germany;

bBASF SE, Synthesis and Homogeneous Catalysis, GCS/C – M313, Carl Bosch Straße 38, 67056 Ludwigshafen, Germany


The direct amination of unactivated alkenes is of particular industrial interest as nitrogen functionalities are widely found in both bulk and fine chemical products.[1] We have previously reported the preparation of novel Pt(II) CNC pincer complexes and their application in a hydrovinylation reaction.[2] In our most recent work,[3] related Pt(II) complexes containing CN- and CNC- based NHC pincer ligands were found to be active in the hydroamination of ethylene with a wide range of amides. The resulting N-ethyl amides are produced in good yields and mostly with Markovnikov selectivity. Additionally, the presence of water increased the reactivity of the Pt(II) complexes derived from bidentate ligands.

[1] Brown, E. G. Ring Nitrogen and Key Biomolecules; Springer: Boston, MA, 1998. [2] D. Serra, P. Cao, J. Cabrera, R. Padilla, F. Rominger, M. Limbach, Organometallics

2011, 30, 1885-1895. [3] P. Cao, J. Cabrera, R. Padilla, D. Serra, F. Rominger, M. Limbach, Organometallics

2012, 31, 921-929.

Poster 29

Intermediates in Iridium-Catalysed Imine Hydrogenation York Schramm, Fabiola Barrios-Landeros, Andreas Pfaltz*

University of Basel, Department of Organic Chemistry, St. Johannsring 19, 4056 Basel, Switzerland e-mail: [email protected]

Hydrogenation of acetophenone- and benzophenone-based N-aryl-imines with

iridium complexes of bidentate P,N-Ligands like A has shown to provide very high enantioselectivities along with full conversion to the corresponding amines.

Acyclic aliphatic N-aryl-imines however still remain challenging substrates with such catalysts as often poor conversion and low enantioselectivites are observed (Figure 1).[1],[2],[3]

N N

N N

30% conv.9% ee

100% conv.20% ee

70% conv.0% ee

100% conv.17% ee

Ph2P N

O

Ir

CH2Cl2, 23°C, 1-100 bar H2, 4-24 h

BArF

N

100% conv.89% ee

A

Figure 1: asymmetric hydrogenation of aryl/alkylketone-derived imines.[1]

We identified new iridium complexes that were formed under reactions conditions.

These complexes were used as catalysts in asymmetric hydrogenation of acyclic aliphatic imines and displayed enhanced enantioselectivity along with significantly increased reactivity. Additional mechanistic investigations by X-Ray crystallography and NMR spectroscopic experiments provided a better understanding of the reaction course. [1] P. Schnider, G. Koch, R. Prétôt, A. Pfaltz, Chem. Eur. J. 1997, 3, 887 [2] A. Baeza, A. Pfaltz, Chem. Eur. J. 2010, 16, 4003 [3] T. C. Nugent, M. El-Shazly, Adv. Synth. Cat., 2010, 352, 753

Poster 30

Josiphos-type ligands bearing a stereogenic P-CF3 moiety and their application in asymmetric hydrogenations

Rino Schwenk, Antonio Togni*

Department of Chemistry and Applied Biosciences, ETH Zürich, CH-8093 Zürich Switzerland


Trifluoromethyl substituents exhibit interesting electronic properties as well as little

steric demand. Josiphos,[1] as a very successful ligand in a broad range of asymmetrically catalyzed reactions,[2] was chosen as backbone for studies on partially electron poor analogues bearing a stereogenic P-CF3 moiety.

The asymmetric hydrogenation of imines applying the corresponding iridium(I) complexes highlighted that a stereogenic phosphorus atom as ligand atom may not only influence the outcome of a reaction.[3] In our case, the stereogenic phosphorus atom vastly controls the sense of chiral induction.

[1] Togni, A. and coworkers, J. Am. Chem. Soc. 1994, 116, 4062-4066. [2] For review, see e.g. Barbaro, P. et al., Coord. Chem. Rev. 2004, 248, 2131-2150. [3] Chen, W. P. et al., J. Am. Chem. Soc. 2006, 128, 3922-3923.

Poster 31

Mechanistic Studies on the Iridium Catalyzed Hydroamination of Strained and Unstrained Aliphatic Alkenes

Christo S. Sevov, John F. Hartwig*

University of California Berkeley


The intermolecular asymmetric hydroamination of unactivated alkenes remains an

unsolved challenge. Iridium complexes of chiral nonracemic bisphosphines were shown to catalyze the hydroamination of norbornene with aryl- and tosyl- amides to produce products in high yields and high enantiomeric excess (ee). The more challenging hydroamination of terminal aliphatic alkenes proceeds with high conversion but poor enantioselectivity. Mechanisms for the iridium-catalyzed hydroamination of bicyclic and terminal alkenes were proposed after kinetic data for the catalytic reaction were gathered and catalytic intermediates were characterized. The resting state species was characterized in the solid and solution state as an iridium(amido)amidate complex that forms following oxidative addition of an N-H bond. From the resting state, reversible dissociation of the amido ligand forms a κ2 bound amidate iridium complex. Catalyst reorganization, possibly formation of the κ1 iridium amidate from the κ2 iridium amidate, is the turnover limiting step (TLS) for the hydroamination of norbornene. The less activated aliphatic alkenes follow a first order rate dependence on the concentration of alkene, which implies that insertion or reductive elimination is the TLS. Deuterium labeling experiments provide evidence for an off-cycle β-hydride elimination step followed by unselective enamine hydrogenation that generates amine products with low ee.


Poster 32

Expanding the Scope of Selective Alkene Oligomerisation Tom E. Stennett, Duncan F. Wass*

School of Chemistry, University of Bristol, Cantock’s Close, Bristol, BS8 1TS, UK


Selective tri- and tetramerisation of ethylene provides an efficient route to 1-hexene

and 1-octene, whereas isoprene can also be trimerised to yield desirable terpenes. Current benchmark oligomerisation catalysts.[1]-[3] require large quantities of an aluminoxane activator, and our aim is to reduce or eliminate this requirement by investigating alternative activation methods. An ionic chromium (III) species, [CrCl2(THF)4][Al(OC4F9)4] (A), has been synthesised and characterised. When combined with diphosphine ligands and 10 equivalents of AlMe3, A yields a species active for the selective oligomerisation of ethylene. Catalyst productivities of up to 2.5x104 g gCr

-1 h-1 were observed, while the excellent selectivities to 1-hexene and 1-octene from the original MAO-activated system[1]-[3] were retained.

Isolation of potentially catalytically relevant bis-chelate Cr complexes during these investigations led us to

consider a class of molybdenum complexes as model compounds. A series of known (B) and novel (C-E) complexes of the form [Mo(N2)2(diphos)2] (diphos = dppe (B),[4] Ph2PN(i-Pr)PPh2 (C), Ph2PN(Me)PPh2 (D) o-(PPh2)2C6H4 (E)) has been synthesised and the compounds’ reactivity towards the alkenes used in selective oligomerisation investigated.

[CrCl2(THF)4][Al(OC4F9)4]

"PNP" ligand10 AlMe3, PhCl

2.5 x 104 g(gCr h)-195% selectivity

3

[1] Carter, A.; Cohen, S.A; Cooley, A.; Murphy, A.; Scutt, J., Wass, D.F.; Chem.

Commun. 2002, 858. [2] Wass, D.F., BP Chemicals Ltd., WO, 02/04119, 2002. [3] Bollmann, A.; Blann, K.; Dixon, J.T.; Hess, F.M.; Killian, E.; Maumela, H.;

McGuinness, D.S.; Morgan, D.H.; Nevelling, A.; Otto, S.; Overett, M.; Slawin, A.M.Z.; Wasserscheid, P.; Kuhlmann, S.; J. Am. Chem. Soc., 2004, 126, 14712

[4] Byrne, J.W.; Blaser, H.U.; Osborn, J.A.; J. Am. Chem. Soc., 1975, 97(13), 3871

Poster 33

Rhodium-Catalysed Hydroformylation of 1,3-Butadiene to Adipic Aldehyde Eszter Takács,a Sebastian Schmidt,b Stuart Smith,a Peter Hofmanna,b*

aCatalysis Research Laboratory CaRLa, Im Neuenheimer Feld 584, 69120 Heidelberg, Germany; bInstitute of Organic Chemistry, University of Heidelberg, Im Neuenheimer Feld 270, 69120 Heidelberg,

Germany


The rhodium-catalysed bis-hydroformylation of 1,3-butadiene has been investigated

both theoretically and experimentally. DFT calculations on the reaction mechanism performed for a novel family of highly n-selective chelating bidentate phosphite ligands predict that in the first hydroformylation step the branched (iso) addition of a rhodium hydride intermediate to 1,3-butadiene is slightly preferred over the normal (n) addition and forms stabile η3-methallyl complexes.[1]

The hydroformylation of these intermediates produces (E/Z)-3-pentenals and further products originating from them. Experimental studies have confirmed that for most ligands this is the dominant reaction pathway; however, the formation of 4-pentenal and 1,6-hexanedial (adipic aldehyde) were also observed. These products result from the normal (n) addition of a rhodium hydride to 1,3-butadiene.[2]

In this part of the research we focus our attention upon the design, synthesis and catalyst screening of new bisphosphite ligands and investigate their suitability as potential ligands in the double hydroformylation reaction of 1,3-butadiene to adipic aldehyde. [1] Schmidt, S. Diploma Thesis, University of Heidelberg 2010. [2] Smith, S.; Rosendahl, T.; Hofmann, P. Organometallics 2011, 30, 3643.

Poster 34

Asymmetric nanocatalysis using N-heterocyclic carbenes as chiral modifiers

Ranganath V. S. Kalluri, Dan-Tam D. Tang, Frank Glorius* Organisch-Chemisches Institut der Westfälischen Wilhelms-Universität Münster, Corrensstraße 40,

48149 Münster, Germany


Various heterogeneous asymmetric catalytic systems have been successfully

developed to overcome problems in homogeneous medium.[1] The activity of a heterogeneous catalyst is dependent on the structure and composition of its surface, which can be both change by variation of the environment.[2] Nanoparticles (NPs) are considered as semi-heterogeneous support since they are readily dispersed in the reaction medium.[3] Although using N-heterocyclic carbenes (NHCs) as ligands has had a tremendous impact on organometallic chemistry in the last years, chiral NHCs have not been explored as chiral modifiers on the surface of NPs to generate a novel heterogeneous catalytic system.[4] Herein, we report the preparation of Pd NPs on the surface of Fe3O4 NPs stabilized by chiral NHCs.[5] The catalytic properties of these surface modified Pd/Fe3O4 NPs which could be magnetically recovered and recycled were evaluated in the α-arylation of ketones exhibiting interesting ees. The details of this reaction and will be discussed and the influence of the modifier will be investigated. [1] Heitbaum, M; Glorius, F.; Escher, I. Angew. Chem. Int. Ed. 2006, 45, 4732-4762. [2] Tao, F.; Grass, M. E.; Zhang, Y.; Butcher, D. R., Renzas, J. R.; Liu, Z.; Chung, J. Y.;

Mun, B. S.; Salmeron, M.; Somarjai, G. A. Science 2008, 322, 932-934. [3] Astruc, D.; Lu, F.; Aranzaes, J. R. Angew. Chem. Int. Ed. 2005, 44, 7852-7872. [4] Glorius, F. NHCs in Transition Metal Catalysis, Ed.; Springer: Berlin, 2007. [5] Ranganath, K.; Kloesges, J.; Schäfer, A.; Glorius, F. Angew. Chem. Int. Ed. 2010, 49,

7786-7789.

Poster 35

Pd-Catalyzed Synthesis of Ar–SCF3 Compounds Under Mild Conditions Georgiy Teverovskiy, David S. Surry, S. L. Buchwald*

Department of Chemistry, Massachusetts Institute of Technology, 77 Massachusetts Avenue, Cambridge,

MA 02139


Aryl trifluoromethyl sulfides (ArSCF3) are an important class of compounds in both

the pharmaceutical and agrochemical areas owing to the capacity of SCF3 to act as a lipophilic electron-withdrawing group. Access to these compounds, however, is complicated by a lack of efficient, safe and general methods. Recent reports from our group regarding novel ligands such as BrettPhos and its analogs have allowed for the successful coupling of weak nucleophiles traditionally thought to be reluctant participants in a typical Pd(0)/(II) catalytic cycle. In light of this, we hypothesized that a similar system might allow for the formation of an aromatic C–SCF3 bond. By using the air and moisture stable AgSCF3 reagent and Ph(Et)3NI in the presence of catalytic amounts of Pd(0)/BrettPhos, we were able to convert a wide range of aryl and heteroaryl bromides into their corresponding aryl trifluoromethyl sulfides under mild conditions and in good to excellent yield. Furthermore, we were able to apply this methodology toward the formal synthesis of Toltrazuril.[1] [1] Teverovskiy, G.; Surry, D. S.; Buchwald, S. L. Angew. Chem., Int. Ed. 2011, 50,

7312-7314.

Poster 36

Catalytic Asymmetric Fischer Indolization Matthew J. Webber, Steffen Müller, Benjamin List*

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

Germany


Since its discovery almost 130 years ago, the Fischer indolization of phenyl

hydrazones has been extensively studied and has consistently proved to be among the most widely used methods for the synthesis of indoles.[1] Despite this interest, no catalytic asymmetric variant had been reported to date. Here we report the first such example, giving access to 3-substituted tetrahydrocarbazoles in high yields and enantioselectivities. Crucial to the method is the removal of the catalyst-poisoning ammonia by-product by an ion exchange resin.[2]

Subsequent studies have shown the method to be applicable to the modular,

enantioselective synthesis of polyaromatic indoles exhibiting helical chirality. [1] Fischer, E.; Jourdan, F. Ber. Dtsch. Chem. Ges. 1883, 16, 2241. [2] Müller, S.; Webber, M. J.; List, B. J. Am. Chem. Soc. 2011, 133, 18534-18537.

Poster 37

Mechanistic Insights into Amidopalladation and Development of New Aerobic Aza-Wacker Palladium Catalysts Utilizing Bidentate Nitrogen Ligands

Paul B. White, Shannon S. Stahl*

Department of Chemistry, University of Wisconsin-Madison e-mail: [email protected]

In recent years, the Stahl group has reported a number of different reactions for

oxidative amidation capable of using molecular oxygen as the stoichiometric oxidant.[1] Amidopalladation of the alkene leads to formation of a carbon-nitrogen bond and is a key step in these catalytic reactions. We have previously obtained evidence that the amidopalladation step proceeds via alkene insertion into a Pd-N bond.[2] This poster will present a series of well-defined (bpy)Pd(II)-sulfonamidate complexes, which have been prepared and shown to react via insertion of a tethered alkene to afford an alkyl-palladium(II) species.[3] These stoichiometric alkene insertion reactions are found to be reversible, and the alkyl-palladium(II) product of this equilibrium undergoes beta-hydride elimination to generate oxidative amination products.

These fundamental studies have provided the basis for our recent pursuit of improved

catalyst systems for aerobic oxidative amidation reactions, employing a Pd(II) salt in combination with an ancillary bidentate nitrogen ligand. Dramatically higher catalytic activity has been observed with a Pd(OAc)2/4,5-diazafluoren-9-one catalyst system.

(tBu2bpy)Pd

SO2ArN

Cl(tBu2bpy)Pd

Cl

SO2ArN SO2Ar

Nk1

k-1+ isomers

k2

NN

tButBu

tBu2bpy =

REVERSIBLEALKENE INSERTION

A B C 00.5

11.5

22.5

3

0 9 18 27 36 45

Con

cent

ratio

n (m

M)

Time (103 s)

A

B

C

[1] a) Fix, S. R.; Brice, J. L.; Stahl, S. S. Angew. Chem. Int. Ed., 2002, 41, 164-166. b)

McDonald, R. I.; Stahl, S. S. Angew. Chem. Int. Ed., 2010, 49, 5529-5532. c) McDonald, R. I.; White, P. B.; Weinstein, A. B.; Tam, C. P.; Stahl, S. S. Org. Lett. 2011, 13, 2830-2833.

[2] Liu, G.; Stahl, S. S. J. Am. Chem. Soc., 2007, 129, 6328-6335. [3] White, P. B.; Stahl, S. S. J. Am. Chem. Soc. 2011, 133, 18594-18597.

Poster 38

Iterative Asymmetric Hydroformylation-Wittig Olefination Gene W. Wong, Clark R. Landis*

Department of Chemistry, University of Wisconsin-Madison, 1101 University Avenue, Madison, WI,

53706


One-pot asymmetric hydroformylation-Wittig olefinations (AHF-WO) yield

structurally diverse alkenes using rhodium-bis-3,4-diazaphospholane catalysts in the presence of a Wittig ylide. The products, γ-chiral α,β-unsaturated carbonyls, constitute useful intermediates in total syntheses. Iterative AHF-WO sequences demonstrate the synthesis of larger complex materials. For example, oligomeric polyesters result from one-pot iterative tandem procedure with a single catalyst loading.

Poster 39

A Mechanistic Investigation of the Chromium-Mediated Bergman Cyclization Kai E. O. Ylijoki,a Séverine Lavy,a Théo Berclaz,b E. Peter Kündiga*

Departments of Organica and Physicalb Chemistry, University of Geneva, 30 Quai Ernest Ansermet, 1211

Geneva 4, Switzerland


The Bergman cyclization of conjugated enediynes has generated significant interest

since the first reports.[1] O’Connor has shown that complexation of an enediyne substrate to a ruthenium or iron transition metal centre results in rapid cycloaromatization at room temperature, yielding metal-arene π-complexes.[2] With our long-standing interest in the preparation and functionalization of early transition metal arene complexes, we report that in the presence of (naphthalene)Cr(CO)3, enediyne substrates readily cycloaromatize at room temperature. To probe the mechanism of this novel process, we have undertaken a combined computational and spectroscopic study to determine the substrate coordination mode and whether a biradical intermediate akin to the thermal Bergman cyclization lies on the potential energy surface.

[1] a) Darby, N.; Kim, C. U.; Salaün, J. A.; Shelton, K. W.; Takada, S.; Masamune, S.

Chem. Commun. 1971, 1516; b) Jones, R. B.; Bergman, R. G. J. Am. Chem. Soc. 1972, 94, 660.

[2] O'Connor, J. M.; Friese, S. J.; Rodgers, B. L. J. Am. Chem. Soc. 2005, 127, 16342.

Lecturer Friedhelm Balkenhohl BASF SE, Synthesis and Homogeneous Catalysis (GCS) Carl-Bosch-Straße 38, 67056 Ludwigshafen, Germany [email protected] Straub Bernd Universität Heidelberg Organisch-Chemisches Institut Im Neuenheimer Feld 270 69120 Heidelberg, Germany [email protected] Christophe Copéret Department of Chemistry ETH Zürich / HCI H 229 Wolfgang-Pauli-Straße 10 8093 Zürich, Switzerland [email protected] Klaus Ditrich BASF SE Carl-Bosch-Strasse GVF/B – A030 67056 Ludwigshafen, Germany [email protected] Deryn E. Fogg Centre for Catalysis Research & Innovation Department of Chemistry University of Ottawa 10 Marie Curie Ottawa, ON Canada; K1N 6N5 [email protected] Gregory C. Fu Department of Chemistry Massachusetts Institute of Technology 77 Massachusetts Avenue, Room 18-290 Cambridge, MA 02139-4307 USA [email protected]

Moshe Kol School of Chemistry Tel Aviv University Tel Aviv 69978; Israel [email protected] Kazushi Mashima Department of Chemistry Graduate School of Engineering Science Osaka University Toyonaka, Osaka 560-8531, Japan [email protected] Warren E. Piers Department of Chemistry University of Calgary 2500 University Dr. NW Calgary, Alberta, CANADA T2N 1N4 [email protected] Dieter Vogt Eindhoven University of Technology Department of Chemical Engineering and Chemistry Helix building, STW 4.34 P.O. Box 513 / Den Dolech 2 5600 MB Eindhoven; The Netherlands [email protected] Christina M. White Department of Chemistry University of Illinois 270 Roger Adams Laboratory 600 South Mathews Ave. Urbana, IL 61801, USA [email protected]

Participants Alexander Arlt Max-Planck-Institut für Kohlenforschung Kaiser-Wilhelm-Platz 1 45470 Mülheim an der Ruhr, Germany [email protected] Nicolas Armanino ETH Zürich Laboratory of Organic Chemistry HCI H335 Wolfgang-Pauli-Strasse 10 8093 Zürich, Switzerland [email protected] Marcel Brill Organisch-Chemisches Institut der Universität Heidelberg Im Neuenheimer Feld 270 69120 Heidelberg, Germany [email protected] Jose Cabrera Catalysis Research Laboratory (CaRLa) Im Neuenheimer Feld 584 69120 Heidelberg, Germany [email protected] Qing-Hai Deng Organisch-Chemisches Institut der Universität Heidelberg Im Neuenheimer Feld 270 69120 Heidelberg, Germany [email protected] Stephanie Dupuy School of Chemistry Purdie Building, North Haugh University of St Andrews St Andrews, KY16 9ST, UK [email protected] Oriol Martinez Ferrate Institute of Chemical Research of Catalonia (ICIQ) Av. Països Catalans 16 43007 Tarragona, Spain [email protected]

Moti Gargir The Weizmann Institute of Science 76100 Rehovot, Israel [email protected] Matthias Grabowski Technische Universität Berlin Fakultät II, Institut für Chemie Straße des 17. Juni 135 10623 Berlin, Germany [email protected] A. Stephen K. Hashmi Organisch-Chemisches Institut der Universität Heidelberg Im Neuenheimer Feld 270 69120 Heidelberg, Germany [email protected] Berit Heggen Max-Planck-Institut für Kohlenforschung Kaiser-Wilhelm-Platz 1 45470 Mülheim an der Ruhr, Germany [email protected] Peter Hofmann Organisch-Chemisches Institut der Universität Heidelberg Lehrstuhl für Organische Chemie III Im Neuenheimer Feld 270 69120 Heidelberg, Germany [email protected] Christoph Hubbert Organisch-Chemisches Institut der Universität Heidelberg Im Neuenheimer Feld 270 69120 Heidelberg, Germany [email protected] Reinhard Jira Kabastastraße 9 81243 München, Germany [email protected]

Takeharu Kageyama Catalysis Research Laboratory (CaRLa) Im Neuenheimer Feld 584 69120 Heidelberg, Germany [email protected] Yanbiao Kang Catalysis Research Laboratory (CaRLa) Im Neuenheimer Feld 584 69120 Heidelberg, Germany [email protected] Andreas Kapelski Institut für Anorganische Chemie RWTH Aachen 52056 Aachen, Germany [email protected] Tillmann Kleine RWTH Aachen University Landoltweg 1 52056 Aachen, Germany [email protected] Christoph Kornhaaß Georg-August-Universität Göttingen Institut für Organische und Biomolekulare Chemie Tammannstrasse 2 37077 Göttingen, Germany [email protected] Michael Lejkowski Catalysis Research Laboratory (CaRLa) Im Neuenheimer Feld 584 69120 Heidelberg, Germany [email protected] Michael Limbach Carl-Bosch-Strasse 38 GCS/C – M313 67056 Ludwigshafen, Germany [email protected] Ronald Lindner Catalysis Research Laboratory (CaRLa) Im Neuenheimer Feld 584 69120 Heidelberg, Germany [email protected]

Neal Mankad Department of Chemistry University of California 619 Latimer Hall Berkeley, CA, 94720-1460, USA [email protected] Sophia Manolikakes Department Chemie und Biochemie Ludwig-Maximilians-Universität Butenandtstraße 5-13 81377 München, Germany [email protected] Ruben Manzano Catalysis Research Laboratory (CaRLa) Im Neuenheimer Feld 584 69120 Heidelberg, Germany [email protected] Claudio Martínez Institute of Chemical Research of Catalonia (ICIQ) Av. Països Catalans 16 43007 Tarragona, Spain [email protected] Juri Möbus Universität Münster Institut für Organische Chemie Corrensstr. 40 48149 Münster, Germany [email protected] Tathagata Mukherjee Department of Chemistry Texas A&M University College Station, TX 77843-3255, USA [email protected] Sharon Neufeldt University of Michigan Department of Chemistry 930 N. University Ann Arbor, MI 48109-1055, USA [email protected]

Boris Neuwald Universität Konstanz Fachbereich Chemie Universitätsstr. 10 78457 Konstanz, Germany [email protected] Carla Obradors Departamento de Química Orgánica Facultad de Ciencias Universidad Autónoma de Madrid Cantoblanco 28049-Madrid, Spain [email protected] Robin Padilla Catalysis Research Laboratory (CaRLa) Im Neuenheimer Feld 584 69120 Heidelberg, Germany [email protected] Philipp Plessow Catalysis Research Laboratory (CaRLa) Im Neuenheimer Feld 584 69120 Heidelberg, Germany [email protected] Manojkumar Poonoth Catalysis Research Laboratory (CaRLa) Im Neuenheimer Feld 584 69120 Heidelberg, Germany [email protected] York Schramm Universität Basel Organische Chemie St. Johanns-Ring 19 4056 Basel, Switzerland [email protected] Rino Schwenk ETH Zürich Laboratorium für Anorganische Chemie HCI H239 Wolfgang-Pauli-Str. 10 8093 Zürich, Switzerland [email protected]

Christo Sevov Department of Chemistry Box 58-6 CLSL A410 University of Illinois 600 South Mathews Ave. Urbana, IL 61801, USA [email protected] Thomas Stennett School of Chemistry University of Bristol Bristol BS8 1TS, UK [email protected] Eszter Tacakz Catalysis Research Laboratory (CaRLa) Im Neuenheimer Feld 584 69120 Heidelberg, Germany [email protected] Daniel Tang Westfälische Wilhelms-Universität Münster Organisch-Chemisches Institut Corrensstrasse 40 48149 Münster, Germany [email protected] Georgiy Teverovskiy Massachusetts Institute of Technology 77 Massachusetts Avenue Cambridge, MA 02139, USA [email protected] Matthew Webber Max-Planck-Institut für Kohlenforschung Kaiser-Wilhelm-Platz 1 45470 Mülheim an der Ruhr, Germany [email protected] Alexander Wetzel Catalysis Research Laboratory (CaRLa) Im Neuenheimer Feld 584 69120 Heidelberg, Germany [email protected]

Paul White Department of Chemistry University of Wisconsin-Madison 1101 University Avenue Madison, Wisconsin 53706-1396, USA [email protected] Kristina Wilckens Catalysis Research Laboratory (CaRLa) Im Neuenheimer Feld 584 69120 Heidelberg, Germany [email protected] Gene Wong Department of Chemistry University of Wisconsin-Madison 1101 University Avenue Madison 53706 WI, USA [email protected] Xuan Ye Catalysis Research Laboratory (CaRLa) Im Neuenheimer Feld 584 69120 Heidelberg, Germany [email protected] Kai Ylijoki Department of Organic Chemistry, University of Geneva - Sciences II, 30, quai Ernest-Ansermet, CH-1211 Geneva 4, Switzerland [email protected]

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Documents

CaRLa Winter School 2008carla-hd.de/wp-content/uploads/2018/02/CaRLaWinterSchool...overwhelming interest in their organic applications has tended to overshadow their inorganic reaction