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<p>The development of olefin hydroacylation with easily accessible acyl reagents in a regioselective manner is highly desirable yet challenging. Herein, we report the hydroacylation of alkenes using acid chlorides as both acyl reagents and endogenous oxidants through a hydrogen atom transfer pathway. Exclusive Markovnikov hydroacylation of a wide range of alkenes, including terminal, internal, 1,1-disubstituted alkenes, and even light gaseous olefins, with aryl and alkyl acid chloride, was achieved with the use of a biquinoline ligand. The direct and step-economy hydroacylation reveals a distinct regioselectivity and ligand dependence compared to traditional NiH chemistry. This protocol has attractive features such as the low cost, broad substrate scope, mild conditions, and easy operation, providing an efficient and modular access to branched ketones with diverse architectures. Density functional theory calculations suggest that the reaction proceeds via a hydrogen atom transfer (HAT) mechanism followed by outer-sphere C-C reductive elimination.</p>

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Hydrogen atom transfer-enabled hydroacylation of alkenes with acyl chlorides

  • 期刊论文

  • 发表日期：

    2025年8月11日

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  • Yi Liu,
  • Guodong Ju,
  • Xueyuan Yan,
  • Jimin Liang,
  • Zhixing Yang,
  • Tao Zhang,
  • Yuan-Qing Xu,
  • Zhong-Yan Cao,
  • Genping Huang,
  • Chao Wang

摘要

The development of olefin hydroacylation with easily accessible acyl reagents in a regioselective manner is highly desirable yet challenging. Herein, we report the hydroacylation of alkenes using acid chlorides as both acyl reagents and endogenous oxidants through a hydrogen atom transfer pathway. Exclusive Markovnikov hydroacylation of a wide range of alkenes, including terminal, internal, 1,1-disubstituted alkenes, and even light gaseous olefins, with aryl and alkyl acid chloride, was achieved with the use of a biquinoline ligand. The direct and step-economy hydroacylation reveals a distinct regioselectivity and ligand dependence compared to traditional NiH chemistry. This protocol has attractive features such as the low cost, broad substrate scope, mild conditions, and easy operation, providing an efficient and modular access to branched ketones with diverse architectures. Density functional theory calculations suggest that the reaction proceeds via a hydrogen atom transfer (HAT) mechanism followed by outer-sphere C-C reductive elimination.