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

Angew Chem Int Ed Engl

Shanghai Key Laboratory of Chemical Biology & School of Pharmacy, East China University of Science and Technology, 130 Meilong Road, Shanghai, 200237, P. R. China.

Published: May 2022


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Article Abstract

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 assistance of computational density functional theory calculations, a Sc/Ir bimetallic catalytic cycle was proposed to illustrate the reaction mechanism.

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http://dx.doi.org/10.1002/anie.202117079DOI Listing

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