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N E W S

New Publication in Angewandte Chemie

 

Stereodivergent and Protecting-Group-Free Synthesis of the Helicascolide Family: A Rhodium-Catalyzed Atom-Economical Lactonization Strategy

 

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All in the family: The natural product family of the helicascolides A–C are one of countless groups of natural products containing six-membered lactones in their core structure. The rhodium-catalyzed regio- and diastereoselective addition of carboxylic acids with allenes permits the atom-economic and highly diastereoselective synthesis of the lactone core and allows for rapid access to this product family.

A. Haydl, D. Berthold, P. A. Spreider, B. Breit, Angew. Chem. 2016, 128, 5859–5863; (link) Angew. Chem. Int. Ed. 2016, 55, 5765–5769. (link)

 

New Publications in Angewandte Chemie and Chemical Science

 

Atom-Economical Dimerization Strategy by the Rhodium-Catalyzed Addition of Carboxylic Acids to Allenes: Protecting-Group-Free Synthesis of Clavosolide A and Late-Stage Modification

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Better late than early: The natural product clavosolide A features a C2-symmetric core. A rhodium-catalyzed dimerization reaction involving the regio- and diastereoselective addition of carboxylic acids to allenes (see scheme) provided rapid access to this complex structure in only eight steps from penta-3,4-dienal and a readily accessible chiral crotyl-transfer reagent. The method is broadly applicable and suited to late-stage diversification.

A. Haydl, B. Breit, Angew. Chem. 2015, 127, 15750–15754; (link) Angew. Chem. Int. Ed. 2015, 54, 15530–15534. (link)

 

Z-Selective Hydrothiolation of Racemic 1,3-Disubstituted Allenes: An Atom-Economic Rhodium-Catalyzed Dynamic Kinetic Resolution

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Zelectivity: The title reaction permits the synthesis of valuable allylic thioethers and sulfones in excellent Z selectivity. By using unsymmetrically 1,3-disubstituted allenes, good to high regioselectivities were obtained. Asymmetric hydrothiolation of racemic allenes with (S,S)-Me-DuPhos meets the criteria of a dynamic kinetic resolution. Me-DuPhos=2′,5′,2′′,5′′-tetramethyl-1,2-bis(phospholanyl)benzene.

A. B. Pritzius, B. Breit, Angew. Chem. 2015, 127, 16044–16048; (link) Angew. Chem. Int. Ed. 2015, 54, 15818–15822. (link)

 

Asymmetric synthesis of allylic amines via hydroamination of allenes with benzophenone imine

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Rhodium-catalyzed highly regio- and enantioselective hydroamination of allenes is reported. Exclusive branched selectivities and excellent enantioselectivities were achieved applying a rhodium(I)/Josiphos catalyst. This method permits the practical synthesis of valuable α-chiral allylic amines using benzophenone imine as ammonia carrier.

K. Xu, Y.-H. Wang, V. Khakyzadeh, Chem. Sci. 2016, articles ASAP; (link)

 

Khwarizmi International Award for Prof. Dr. Bernhard Breit

 

The Iranian Research Organization for Science and Technology (IROST), affiliated to the Iranian Ministry of Science, Research and Technology, is awarding the Khwarizmi International Award to Prof. Breit for his dedication, excellence and sustained hard work in the field of research. Since 1987, the KIA is presented to scientists for outstanding achievements and innovations that advance science and technology. It is the most important Iranian distinction of its kind and is presented by the President of Iran, Hassan Rouhani, and the Iranian Minister for Science, Research and Technology.

The award ceremony took place on 7 March 2016 in Iran’s capital Tehran in the presence of Prof. Breit. He is staying in Iran for several days and will present his research at renowned Iranian universities and institutions.

 link

Sustainable catalysts: a German-Japanese cooperation combines the strong points of the University of Freiburg and expertise from Nagoya

Nagoya_Freiburg

The project “Multicomponent Supramolecular Catalysts for Sustainable Chemical Synthesis” conducted by Prof. Dr. Bernhard Breit (University of Freiburg), Prof. Dr. Takashi Ooi and Prof. Dr. Kenichiro Itami (Nagoya University) tackles the development of environmentally friendly and energy-efficient catalysts. Catalysts are substances that increase the rate of a chemical reaction by minimizing the required amount of activation energy, an energetic barrier between chemical reaction partners. During this process, the catalysts themselves are not consumed.

Around 80 percent of all chemical products are manufactured using catalytic processes. This means that increased environmental compatibility and energy efficiency of catalysts entails direct positive effects in the manufacture of chemical and pharmaceutical products. The project group draws inspiration from natural catalysts, such as enzymes, and aims to develop a new generation of supramolecular catalysts. Furthermore, the group’s groundbreaking research is to lay the basis for an international graduate school.

 link

New Postdoctoral position in Organic Synthesis/Medicinal Chemistry

The research group of Prof. Breit at the Institute for Organic Chemistry is offering a

Postdoctoral position in Organic Synthesis/Medicinal Chemistry

At the Institute of Organic Chemistry at the Albert-Ludwigs University Freiburg in the research group of Professor Breit a postdoctoral position is available. The position is sponsored by the collaborative research center “Medical Epigenetics - SFB992“ and is part of a team consisting of structural biology and bioinformatics. The scientific goals are to synthesize small target molecules (primarily heterocyclic structures) and to evaluate within this team the biological properties, binding properties towards epigenetic target proteins in order to identify new molecular probes. Extensive experience in preparative organic chemistry including multistep synthesis is expected.

Please send a letter of motivation, a complete CV, a summary of research achievements and two letters of recommendation to Prof. Dr. Bernhard Breit.

 e-mail

New Publication in Nature Communications

 

Asymmetric synthesis of N-allylic indoles via regio- and enantioselective allylation of aryl hydrazines

 

                                187abstract

The asymmetric synthesis of N-allylic indoles is important for natural product synthesis and pharmaceutical research. The regio- and enantioselective N-allylation of indoles is a true challenge due to the favourable C3-allylation. We develop here a new strategy to the asymmetric synthesis of N-allylic indoles via rhodium-catalysed N-selective coupling of aryl hydrazines with allenes followed by Fischer indolization. The exclusive N-selectivities and good to excellent enantioselectivities are achieved applying a rhodium(I)/DTBM-Segphos or rhodium(I)/DTBM-Binap catalyst. This method permits the practical synthesis of valuable chiral N-allylated indoles, and avoids the N- or C-selectivity issue.

K. Xu, T. Gilles, B. Breit, Nat. Commun., 2015, 6, 7616; (link)

 

New Publication in Journal of the American Chemical Society

 

Enantioselective Redox-Neutral Rh-Catalyzed Coupling of Terminal Alkynes with Carboxylic Acids Toward Branched Allylic Esters

 

 

We report on the first enantioselective variant of the atom-economic and redox-neutral coupling of carboxylic acids with terminal alkynes under rhodium catalysis utilizing the chiral, bidentate (R,R)-Cp-DIOP ligand. This represents the first example of this convenient asymmetric access to valuable branched allylic esters. The utility of this methodology is demonstrated by both a reaction performed on large scale and a short three-step synthesis of two naturally occurring γ-butyrolactones. A stereochemical model explaining the observed absolute configuration of the products based on DFT calculations is given.

P. Koschker, M. Kähny, B. Breit, J. Am. Chem. Soc., 2015, 137 (8), 3131–3137; (link)

 

35th Regiosymposium 2015

 

 35th Regiosymposium 2015

 

New Publication in Angewandte Chemie

 

Asymmetric Rhodium-Catalyzed Addition of Thiols to Allenes: Synthesis of Branched Allylic Thioethers and Sulfones

 

All about S: The rhodium-catalyzed enantioselective hydrothiolation of terminal monosubstituted allenes with aromatic and functionalized aliphatic thiols permits the atom-economic synthesis of valuable branched allylic thioethers and sulfones in high regio- and enantioselectivity. By varying the ligand and reaction conditions both aromatic and aliphatic thiols were tolerated.

A. B. Pritzius, B. Breit, Angew. Chem. 2015, 127, 3164-3168; (link) Angew. Chem. Int. Ed. 2015, 54, 3121-3125. (link)

 

 

 

New Publication in Angewandte Chemie

 

Rhodium-Catalyzed Chemo-, Regio-, and Enantioselective Addition of 2-Pyridones to Terminal Allenes

 

A rhodium-catalyzed chemo-, regio-, and enantioselective addition of 2-pyridones to terminal allenes to give branched N-allyl 2-pyridones is reported. Preliminary mechanistic studies support the hypothesis that the reaction is initiated from the more acidic 2-hydroxypyridine form, and the initial kinetic O-allylation product was finally converted into the thermodynamically more stable N-allyl 2-pyridone.

C. Li, M. Kähny, B. Breit, Angew. Chem. 2014, 126, 14000-14004; (link) Angew. Chem. Int. Ed. 2014, 53, 13780-13784. (link )

 

 

 

 

New VIP-Publication in Angewandte Chemie

 

Unlocking the N2 Selectivity of Benzotriazoles: Regiodivergent and Highly Selective Coupling of Benzotriazoles with Allenes

 

Ligand control: Exceptionally high N2 and N1 selectivities have been achieved in the rhodium-catalyzed coupling of benzotriazoles with allenes by using DPEphos and JoSPOphos, respectively (see scheme). This method permits the atom-economic synthesis of valuable branched N2- and N1-allylated benzotriazole derivatives.

K. Xu, N. Thieme, B. Breit, Angew. Chem. 2014, 126, 7396-7399; (link) Angew. Chem. Int. Ed. 2014, 53, 7268-7271. (link)

 

New Publication in Angewandte Chemie

 

Atom-Economic, Regiodivergent, and Stereoselective Coupling of Imidazole Derivatives with Terminal Allenes

 

Taking control:New Rh- and Pd-catalyzed regiodivergent and stereoselective intermolecular coupling reactions of imidazole derivatives with monosubstituted allenes are reported. Using a RhI/Josiphos system, perfect regioselectivities and high enantiomeric excess were obtained, while a PdII/dppf system gave the linear products with high regioselectivities and high E/Z selectivities. dppf=1,1′-bis(diphenylphosphino)ferrocene, Josiphos=(R)-1-[(Sp)-2-(dicyclohexylphosphino)ferrocenyl]ethyldialkylphosphine.

K. Xu, N. Thieme, B. Breit, Angew. Chem. 2014, 126, 2194-2197; (link) Angew. Chem. Int. Ed. 2014, 53, 2162-2165. (link)

 

 

New Publications in Journal of the American Chemical Society

 

(1) Rhodium-Catalyzed Chemo- and Regioselective Decarboxylative Addition of β-Ketoacids to Allenes: Efficient Construction of Tertiary and Quaternary Carbon Centers

 

 

A rhodium-catalyzed chemo- and regioselective intermolecular decarboxylative addition of β-ketoacids to terminal allenes is reported. Using a Rh(I)/DPPF system, tertiary and quaternary carbon centers were formed with exclusively branched selectivity under mild conditions. Preliminary mechanism studies support that the carbon–carbon bond formation precedes the decarboxylation and the reaction occurs in an outer-sphere mechanism.

C. Li, B. Breit, J. Am. Chem. Soc., 2014, 136 (3), 862–865; (link)

 

(2) Mechanistic Investigations of the Rhodium Catalyzed Propargylic CH Activation

 

 

Previously we reported the redox-neutral atom economic rhodium catalyzed coupling of terminal alkynes with carboxylic acids using the DPEphos ligand. We herein present a thorough mechanistic investigation applying various spectroscopic and spectrometric methods (NMR, in situ-IR, ESI-MS) in combination with DFT calculations. Our findings show that in contrast to the originally proposed mechanism, the catalytic cycle involves an intramolecular protonation and not an oxidative insertion of rhodium in the OH bond of the carboxylic acid. A σ-allyl complex was identified as the resting state of the catalytic transformation and characterized by X-ray crystallographic analysis. By means of ESI-MS investigations we were able to detect a reactive intermediate of the catalytic cycle.

U. Gellrich, A. Meißner, A. Steffani, M. Kähny, H.-J. Drexler, D. Heller, D. A. Plattner, B. Breit, J. Am. Chem. Soc., 2014, 136 (3), 1097–1104; (link)

 

New Publication in Chemistry - A European Journal

 

Realistic Energy Surfaces for Real-World Systems: An IMOMO CCSD(T):DFT Scheme for Rhodium-Catalyzed Hydroformylation with the 6-DPPon Ligand

 

A two-layer model (CCSD(T):DFT) in the framework of an integrated molecular orbital plus molecular orbital (IMOMO) scheme (see figure) was evaluated for rhodium-catalyzed hydroformylation with the self-assembling 6-diphenylphosphinopyridine-(2H)-1-one ligand (6-DPPon). By applying the energetic-span model, an excellent match between the calculated and experimentally observed turnover frequencies was achieved.

U. Gellrich, D. Himmel, M. Meuwly, B. Breit, Chem. Eur. J. 2013, 19, 16272-16281; (link)

 

New Publications in Angewandte Chemie

 

(1) Catalytic Asymmetric Synthesis of Allylic Alcohols and Derivatives and their Applications in Organic Synthesis

 

Allylic alcohols represent an important and highly versatile class of chiral building blocks for organic synthesis. This Review summarizes the plethora of methods developed for the catalytic asymmetric synthesis of enantioenriched allylic alcohols. These include: dynamic kinetic resolution (DKR/DKAT), nucleophilic 1,2-addition to carbonyl groups, allylic substitution, oxidation of C[BOND]H bonds, the addition of O nucleophiles to π systems, reduction of unsaturated carbonyl compounds, and an alternative route from enantioenriched propargylic alcohols. Furthermore, these catalytic asymmetric processes are exemplified by their applications in the syntheses of complex molecules such as natural products and potential therapeutic agents.

M. A. Lumbroso, M. L. Cooke, B. Breit, Angew. Chem. 2013, 125, 1942–1986; (link) Angew. Chem. Int. Ed. 2012, 51, 1890–1932. (link)

 

(2) Catalytic Hydrogenation of Amides to Amines under Mild Conditions

Under (not so much) pressure : A general method for the hydrogenation of tertiary and secondary amides to amines with excellent selectivity using a bimetallic Pd–Re catalyst has been developed. The reaction proceeds under low pressure and comparatively low temperature. This method provides organic chemists with a simple and reliable tool for the synthesis of amines.

U. M. Stein, B. Breit, Angew. Chem. 2013, 125, 2287-2290; (link) Angew. Chem. Int. Ed. 2013, 52, 2231-2234. (link)

 

 

 

 

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