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<p>In this work, the Se-π acid-catalyzed oxidative ring-closing reaction of (<i>E</i>)-4-phenylbut-3-enoic acid promoted by either 2-iodosobenzoic acid (<b>IBA</b>) or 3,4,5,6-tetrafluoro-2-iodosobenzoic acid (<b>FIBA</b>) was theoretically studied at PBE0-D3(BJ)/Def2-TZVP/SMD(MeCN)//PBE0-D3(BJ)/Def2-SVP/SMD(MeCN) level of theory. The most likely reaction mechanisms were screened out, catalytic cycles were proposed, and the rate-determining steps and the activation Gibbs energy barriers of all the catalytic cycles were investigated. The acidity of breaking C-H bonds determines the regioselectivity of the <i>β</i>-elimination reaction. The reasons why the structural differences between <b>IBA</b> and <b>FIBA</b> lead to different reaction yields have also been discussed in detail.</p>

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A theoretical study of organoselenium-catalyzed oxidative ring-closing reaction: structure/selectivity/yield relationships

  • 期刊论文

  • 发表日期：

    2025年8月23日

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  • Chao-Xian Yan,
  • Yuan Lei,
  • Xin Wei,
  • Ling-Jian Yang,
  • Xin-Qiang Hua

摘要

In this work, the Se-π acid-catalyzed oxidative ring-closing reaction of (E)-4-phenylbut-3-enoic acid promoted by either 2-iodosobenzoic acid (IBA) or 3,4,5,6-tetrafluoro-2-iodosobenzoic acid (FIBA) was theoretically studied at PBE0-D3(BJ)/Def2-TZVP/SMD(MeCN)//PBE0-D3(BJ)/Def2-SVP/SMD(MeCN) level of theory. The most likely reaction mechanisms were screened out, catalytic cycles were proposed, and the rate-determining steps and the activation Gibbs energy barriers of all the catalytic cycles were investigated. The acidity of breaking C-H bonds determines the regioselectivity of the β-elimination reaction. The reasons why the structural differences between IBA and FIBA lead to different reaction yields have also been discussed in detail.