Synergistic Ir/Cu Catalysis For Asymmetric Allylic Alkylation Of Oxindoles: Enantio- And Diastereoselective Construction Of Quaternary And Tertiary Stereocenters

CHEMISTRY-A EUROPEAN JOURNAL(2021)

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摘要
3,3-Disubstituted oxindoles bearing quaternary and tertiary stereogenic centers are privileged structural motifs, which widely exist in pharmaceutical and natural products. Herein, a highly regio-, enantio-, and diastereoselective allylic alkylation of 3-alkyl oxindoles through synergistic iridium and copper catalysis is described, which provides a series of 3,3-disubstituted oxindole derivatives containing adjacent quaternary and tertiary stereogenic centers in excellent yields, enantiomeric excess, and diastereomeric ratio (for 30 examples, up to 97% yield, > 99% ee, and > 20: 1 dr). This method provides exclusive branched selectivity, excellent enantio- and diastereoselectivities, and good functional compatibility. Control experiments suggested that the chiral copper catalyst is required for achieving high reactivities and diastereoselectivities under mild reaction conditions.
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alkylation, asymmetric catalysis, bimetallic catalysis, oxindoles, quaternary stereogenic centers
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