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

Enantioselective γ-Alkylation of α,β-Unsaturated Malonates and Ketoesters by a Sequential Ir-Catalyzed Asymmetric Allylic Alkylation/Cope Rearrangement.
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DOI:
10.1021/jacs.6b02153
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发表时间:
2016-04-27
影响因子:
15
通讯作者:
Stoltz BM
Stoltz BM
中科院分区:
化学1区
文献类型:
--
作者:
Liu WB;Okamoto N;Alexy EJ;Hong AY;Tran K;Stoltz BM

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报道了α,β-不饱和丙二酸酯和酮酯的催化、对映选择性γ -烷基化反应。这种策略需要铱催化的扩展烯醇化物的高度区域选择性和对映选择性α-烷基化,以及随后通过科普重排将手性转移到γ-位。
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.