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<p>Atom transfer radical addition (ATRA) of aroyl chlorides to access β-chloroacyl derivatives via photoredox catalysis remains hamstrung by the need to use precious iridium photocatalysts and activated alkenes as acceptors. Here we report a unified platform for the regioselective chlorocarbonylation of alkenes via visible-light-mediated ATRA of aroyl chlorides catalysed by a heteroleptic Cu(I) complex featuring extensive substrate scope, scalability and functional group tolerance. In addition, alkynes are amenable substrates, allowing <i>E</i>-selective β-chlorovinyl ketone formation. The synthetic utility of the protocol is demonstrated through the functionalization of complex substrates, post-modifications of the products and the formal synthesis of pharmacologically relevant haloperidol, seratrodast and the naturally occurring piperidine alkaloid (−)-sedamine. This study undergirds the exclusive role of a heteroleptic copper(I) complex, which outperforms homoleptic copper(I) complexes—efficient for many ATRA processes—owing to its longer excited-state lifetime and adaptive ligand environment being tailored for the distinctive mechanistic steps catalysed by Cu(I) and Cu(II) in the title reaction.</p><p></p>

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A general photocatalytic platform for the regio- and stereoselective β-chloroacylation of alkenes and alkynes using a heteroleptic copper(I) complex

  • 期刊论文

  • 出版模式：

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  • 发表日期：

    2025年6月24日

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  • Tirtha Mandal,
  • Mangish Ghosh,
  • Hendrik Paps,
  • Tanumoy Mandal,
  • Oliver Reiser

摘要

Atom transfer radical addition (ATRA) of aroyl chlorides to access β-chloroacyl derivatives via photoredox catalysis remains hamstrung by the need to use precious iridium photocatalysts and activated alkenes as acceptors. Here we report a unified platform for the regioselective chlorocarbonylation of alkenes via visible-light-mediated ATRA of aroyl chlorides catalysed by a heteroleptic Cu(I) complex featuring extensive substrate scope, scalability and functional group tolerance. In addition, alkynes are amenable substrates, allowing E-selective β-chlorovinyl ketone formation. The synthetic utility of the protocol is demonstrated through the functionalization of complex substrates, post-modifications of the products and the formal synthesis of pharmacologically relevant haloperidol, seratrodast and the naturally occurring piperidine alkaloid (−)-sedamine. This study undergirds the exclusive role of a heteroleptic copper(I) complex, which outperforms homoleptic copper(I) complexes—efficient for many ATRA processes—owing to its longer excited-state lifetime and adaptive ligand environment being tailored for the distinctive mechanistic steps catalysed by Cu(I) and Cu(II) in the title reaction.