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<p>The <i>Z</i>/<i>E</i> configuration of alkenes profoundly influences their chemical and biological properties. Direct synthesis of thermodynamically less favorable (<i>Z</i>)-vinyl sulfonamides represents a significant challenge in organic synthesis. This study introduces a novel copper-catalyzed hydrosulfamoylation of alkynes, using SO<sub>2</sub>, trimethylsilylhydride [(TMS)<sub>3</sub>SiH], and electrophilic amines in a straightforward manner, which enables the stereoselective <i>anti</i>-Markovnikov synthesis of (<i>Z</i>)-vinyl sulfonamides by leveraging kinetic controls. This methodology effectively yields diverse (<i>Z</i>)-vinyl sulfonamides with excellent regioselectivity and stereoselectivity, compatible with aryl alkynes as well as primary and secondary amines. Density functional theory (DFT) calculations underscore the vinyl radical as a crucial intermediate, whose kinetic-based transformation dictates the stereoselectivity of the resulting products. This research not only presents a robust strategy for synthesizing (<i>Z</i>)-vinyl sulfonamides but also advances the understanding of the (<i>Z</i>)-isomerization mechanism.</p>

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Stereoselective synthesis of (Z)-vinyl sulfonamides via kinetically controlled hydrosulfamoylation of alkynes

  • 期刊论文

  • 发表日期：

    2025年10月29日

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  • Haiping Lv,
  • Xinzhou Chen,
  • Xiaochun He,
  • Xuemei Zhang,
  • Zhong Lian

摘要

The Z/E configuration of alkenes profoundly influences their chemical and biological properties. Direct synthesis of thermodynamically less favorable (Z)-vinyl sulfonamides represents a significant challenge in organic synthesis. This study introduces a novel copper-catalyzed hydrosulfamoylation of alkynes, using SO2, trimethylsilylhydride [(TMS)3SiH], and electrophilic amines in a straightforward manner, which enables the stereoselective anti-Markovnikov synthesis of (Z)-vinyl sulfonamides by leveraging kinetic controls. This methodology effectively yields diverse (Z)-vinyl sulfonamides with excellent regioselectivity and stereoselectivity, compatible with aryl alkynes as well as primary and secondary amines. Density functional theory (DFT) calculations underscore the vinyl radical as a crucial intermediate, whose kinetic-based transformation dictates the stereoselectivity of the resulting products. This research not only presents a robust strategy for synthesizing (Z)-vinyl sulfonamides but also advances the understanding of the (Z)-isomerization mechanism.