Regio- and Enantioselective γ-Allylic Alkylation of In-Situ-Generated Free Dienolates via Scandium/Iridium Dual Catalysis.

Regio- and Enantioselective γ-Allylic Alkylation of In-Situ-Generated Free Dienolates via Scandium/Iridium Dual Catalysis.
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DOI:
10.1002/anie.202117079
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发表时间:
2022
期刊:
Angewandte Chemie
影响因子:
--
通讯作者:
Wei-Ping Deng
Wei-Ping Deng
中科院分区:
--
文献类型:
--
作者:
Jian Zhang;Wu-Lin Yang;Hanliang Zheng;Yi Wang;Wei-Ping Deng

文献摘要

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An unprecedented asymmetric γ -allylic alkylation of free dienolates via Sc/Ir dual catalysis is reported, which affords a range of synthetically versatile γ -allylic crotonaldehydes in high efficiency with excellent chemo-, regio-, and enantioselectivities. The dienolates bearing no essential auxiliary groups were generated in-situ by scandium triflate-mediated Meinwald rearrangement of vinyloxiranes atom-economically. With the assist of computational density functional theory calculations, a Sc/Ir bimetallic catalytic cycle was proposed to illustrate the reaction mechanism.