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

作者：Wenbo Liu, Noriko Okamoto, Eric J. Alexy, Allen Y. Hong, Kristy Tran, Brian M. Stoltz · 发表于：Journal of the American Chemical Society · 年份：2016 · DOI：10.1021/jacs.6b02153 · 被引用次数：117 · 研究领域：Asymmetric Synthesis and Catalysis、Asymmetric Hydrogenation and Catalysis、Synthetic Organic Chemistry Methods

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