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<p>Divergent synthesis approaches generate all isomers of a molecule, but typically focus on single-dimensional selectivity control. The more challenging two-dimensional divergent synthesis dictating two types of selectivity to achieve all four isomers has recently received some attention. As such, three-dimensional divergent synthesis through dictation of three types of selectivity to prepare eight isomers or analogues is very challenging. Here we report a catalyst-controlled three-dimensional divergent protocol for the synthesis of eight types of diaryl allyl skeleton (through combinations of <i>E</i>/<i>Z</i> and <i>R</i>/<i>S</i> stereochemistry and 1,1-/1,3-substitution patterns) from the reaction of alkynes and heteroarenes. Good geometric selectivity, regioselectivity and enantioselectivity are observed for the hydroheteroarylation process of internal alkynes with indolizines via Pd and Rh catalysis. Experimental data and density functional theory calculations reveal that the Pd and Rh catalysts have differing mechanistic pathways for the hydroarylation of the internal alkynes and corresponding allene intermediates.</p><p></p>

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Three-dimensional divergent hydroheteroarylation of internal alkynes with indolizines

  • 期刊论文

  • 发表日期：

    2025年9月3日

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  • Ao Huang,
  • Hao-Ran Xu,
  • Zi-Jiang Yang,
  • Xiao-Song Xue,
  • Zhi-Tao He

摘要

Divergent synthesis approaches generate all isomers of a molecule, but typically focus on single-dimensional selectivity control. The more challenging two-dimensional divergent synthesis dictating two types of selectivity to achieve all four isomers has recently received some attention. As such, three-dimensional divergent synthesis through dictation of three types of selectivity to prepare eight isomers or analogues is very challenging. Here we report a catalyst-controlled three-dimensional divergent protocol for the synthesis of eight types of diaryl allyl skeleton (through combinations of E/Z and R/S stereochemistry and 1,1-/1,3-substitution patterns) from the reaction of alkynes and heteroarenes. Good geometric selectivity, regioselectivity and enantioselectivity are observed for the hydroheteroarylation process of internal alkynes with indolizines via Pd and Rh catalysis. Experimental data and density functional theory calculations reveal that the Pd and Rh catalysts have differing mechanistic pathways for the hydroarylation of the internal alkynes and corresponding allene intermediates.