Deracemization of Quaternary Stereocenters by Pd-Catalyzed Enantioconvergent Decarboxylative Allylation of Racemic β-Ketoesters

Justin T. Mohr, Douglas C. Behenna, Andrew M. Harned, Brian M. Stoltz*

*The Arnold and Mabel Beckman Laboratories of Chemical Synthesis, Division of Chemistry and Chemical Engineering, California Institute of Technology, 1200 E. California Boulevard, MC 164-30, Pasadena, CA 91125, USA, Email: stoltzcaltech.edu

J. T. Mohr, D. C. Behenna, A. M. Harned, B. M. Stoltz, Angew. Chem. Int. Ed., 2005, 44, 6924-6927.

DOI: 10.1002/anie.200502018

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Abstract

A catalytic enantioconvergent synthesis of quaternary stereocenters from racemates with quaternary stereocenters has been developed. A chiral Pd catalyst is involved in both the stereoablative (C-C bond-breaking) and stereoselective (C-C bond-forming) steps.

see article for more examples

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Development of (Trimethylsilyl)ethyl Ester Protected Enolates and Applications in Palladium-Catalyzed Enantioselective Allylic Alkylation: Intermolecular Cross-Coupling of Functionalized Electrophiles

C. M. Reeves, D. C. Behenna, B. M. Stoltz, Org. Lett., 2014, 16, 2314-2317.

The Enantioselective Tsuji Allylation

D. C. Behenna, B. M. Stoltz, J. Am. Chem. Soc., 2004, 126, 15044-15045.

Catalytic Enantioselective Decarboxylative Protonation

J. T. Mohr, T. Nishimata, D. C. Behenna, B. M. Stoltz, J. Am. Chem. Soc., 2006, 128, 11348-11349.

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Key Words

allylation, Tsuji-Trost Reaction, asymmetric catalysis, enolates, palladium

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ID: J06-Y2005-1670