4.8 Article

Enantioselective γ-Alkylation of α,β-Unsaturated Malonates and Ketoesters by a Sequential Ir-Catalyzed Asymmetric Allylic Alkylation/Cope Rearrangement

Journal

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
Volume 138, Issue 16, Pages 5234-5237

Publisher

AMER CHEMICAL SOC
DOI: 10.1021/jacs.6b02153

Keywords

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Funding

  1. NIH-NIGMS [R01GM080269]
  2. Gordon and Betty Moore Foundation
  3. Caltech
  4. Shanghai Institute of Organic Chemistry (SIOC)
  5. Hiroshima International University
  6. National Science Foundation
  7. California HIV/AIDS Research Program [F08-CT-201]

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A catalytic, enantioselective gamma-alkylation of alpha,beta-unsaturated malonates and ketoesters is reported. This strategy entails a highly regio- and enantioselective iridium-catalyzed alpha-alkylation of an extended enolate, and a subsequent translocation of chirality to the gamma-position via a Cope rearrangement.

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