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<p>Asymmetric remote difunctionalization of alkenes is a longstanding challenge in synthetic chemistry, offering the potential to install two functional groups simultaneously across distal carbon atoms in a stereocontrolled manner. While ingenious strategies have been devised to achieve this transformation, a general catalytic system for remote, enantioselective hetero-carbofunctionalization <i>and</i> dicarbofunctionalization of alkenes has remained elusive. Here, we present a nickel/photoredox dual-catalyzed asymmetric remote 1,5-carbosulfonylation and 1,5-dicarbofunctionalization of vinyl cyclopropanes. This cascade reaction integrates radical addition, C–C bond cleavage, and cross-coupling to functionalize two distal carbon atoms with high enantioselectivity. Our protocol demonstrates broad substrate scope, excellent functional group tolerance, and significant synthetic utility, as evidenced by late-stage functionalization and product derivatization. Our mechanistic investigations support the involvement of a Ni(0)/Ni(I)/Ni(III) catalytic cycle in our system. This work establishes a versatile platform for remote alkene difunctionalization, expanding the toolbox of enantioselective synthetic methods and unlocking new avenues for complex molecule construction.</p>

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Vinyl cyclopropanes as a unifying platform for enantioselective remote difunctionalization of alkenes

  • 期刊论文

  • 出版模式：

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  • 发表日期：

    2025年7月29日

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  • Xiaoyong Du,
  • Marc E. Lennon,
  • Georgia Kriticou,
  • Cristina Nevado

摘要

Asymmetric remote difunctionalization of alkenes is a longstanding challenge in synthetic chemistry, offering the potential to install two functional groups simultaneously across distal carbon atoms in a stereocontrolled manner. While ingenious strategies have been devised to achieve this transformation, a general catalytic system for remote, enantioselective hetero-carbofunctionalization and dicarbofunctionalization of alkenes has remained elusive. Here, we present a nickel/photoredox dual-catalyzed asymmetric remote 1,5-carbosulfonylation and 1,5-dicarbofunctionalization of vinyl cyclopropanes. This cascade reaction integrates radical addition, C–C bond cleavage, and cross-coupling to functionalize two distal carbon atoms with high enantioselectivity. Our protocol demonstrates broad substrate scope, excellent functional group tolerance, and significant synthetic utility, as evidenced by late-stage functionalization and product derivatization. Our mechanistic investigations support the involvement of a Ni(0)/Ni(I)/Ni(III) catalytic cycle in our system. This work establishes a versatile platform for remote alkene difunctionalization, expanding the toolbox of enantioselective synthetic methods and unlocking new avenues for complex molecule construction.