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<p>The 1,n-metal migration process is distinct from traditional bond-forming pathways and offers a unique approach for constructing complex organic architectures. However, in contrast to the well-documented Pd-, Rh-, Fe-, Co-, and Ni-catalyzed migration coupling reactions, studies on Cu-catalyzed variants are scarce. This report describes density functional theory (DFT) calculations aiming to investigate the mechanism of Cu-catalyzed formal hydro(borylmethylsilyl)ation, which is proposed to occur via 1,4-copper migration. The computational results support a metal non-migration mechanism. The stereoselectivity of the reaction is determined by the energy difference between the proton transfer transition state and the anionic releasing transition state after syn-to-anti isomerization. Additionally, DFT calculations were used to evaluate the effects of various substituents on the internal alkyne. Overall, this study offers a solid theoretical basis for experimental investigations into Cu-catalyzed migration coupling reactions.</p><p></p>

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A theoretical study on the feasibility of 1,4-Copper migration in the Cu-catalyzed formal hydro(borylmethylsilyl)ation of internal alkynes

  • 期刊论文

  • 出版模式：

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  • 发表日期：

    2025年12月9日

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  • Song Liu,
  • Wei Chen,
  • Xinyu Long,
  • Dianmin Zhang,
  • Jingxu Chen,
  • Zhou Zhu,
  • Haobin Wei

摘要

The 1,n-metal migration process is distinct from traditional bond-forming pathways and offers a unique approach for constructing complex organic architectures. However, in contrast to the well-documented Pd-, Rh-, Fe-, Co-, and Ni-catalyzed migration coupling reactions, studies on Cu-catalyzed variants are scarce. This report describes density functional theory (DFT) calculations aiming to investigate the mechanism of Cu-catalyzed formal hydro(borylmethylsilyl)ation, which is proposed to occur via 1,4-copper migration. The computational results support a metal non-migration mechanism. The stereoselectivity of the reaction is determined by the energy difference between the proton transfer transition state and the anionic releasing transition state after syn-to-anti isomerization. Additionally, DFT calculations were used to evaluate the effects of various substituents on the internal alkyne. Overall, this study offers a solid theoretical basis for experimental investigations into Cu-catalyzed migration coupling reactions.