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

Stereochemical alchemy! Racemic allyl β‐ketoesters allow the regiocontrolled formation of enolates, where the same catalyst is intimately involved in both the stereoablative (CC bond‐breaking) and stereoselective (CC bond‐forming) steps. This mechanistic and practical insight led to the formation...

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Published inAngewandte Chemie (International ed.) Vol. 44; no. 42; pp. 6924 - 6927
Main Authors Mohr, Justin T., Behenna, Douglas C., Harned, Andrew M., Stoltz, Brian M.
Format Journal Article
LanguageEnglish
Published Weinheim WILEY-VCH Verlag 28.10.2005
WILEY‐VCH Verlag
Wiley
Subjects
Alkylation
allylation
asymmetric catalysis
Catalysis
Chemistry
Chemistry, Multidisciplinary
Decarboxylation
enolates
Esters - chemical synthesis
Ketones - chemical synthesis
Molecular Structure
Organometallic Compounds - chemistry
palladium
Palladium - chemistry
Physical Sciences
Science & Technology
Stereoisomerism
REARRANGEMENT
ASYMMETRIC-SYNTHESIS
ARYLATION
palladium
enolates
asymmetric catalysis
allylation
DYNAMIC KINETIC RESOLUTION
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Summary:Stereochemical alchemy! Racemic allyl β‐ketoesters allow the regiocontrolled formation of enolates, where the same catalyst is intimately involved in both the stereoablative (CC bond‐breaking) and stereoselective (CC bond‐forming) steps. This mechanistic and practical insight led to the formation of multiple quaternary carbon stereocenters in a single cascade reaction (see scheme).
Bibliography:istex:2EB430F33E26BFB3312EA99B268FBFB11960C1AE
ark:/67375/WNG-BP3D0MHT-4
ArticleID:ANIE200502018
The authors wish to thank the Fannie and John Hertz Foundation (predoctoral fellowship to D.C.B.), the NIH (postdoctoral fellowship to A.M.H.), Research Corporation, the Camille and Henry Dreyfus Foundation, Merck, Pfizer, and Lilly for financial support, and Prof. D. A. Dougherty for helpful discussions.
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ISSN:1433-7851
1521-3773
DOI:10.1002/anie.200502018