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<p>Sulfur-stereogenic motifs are important in natural products, pharmaceuticals, agrochemicals and chiral ligands and catalysts, and are increasingly explored in functional materials. Direct enantioselective S-alkylation using non-prochiral C(<i>sp</i><sup>3</sup>)–H bonds, particularly unactivated ones, offers an ideal atom-economical route to sulfur-stereogenic centres, yet remains highly challenging as their activation typically requires strong oxidants, and chemo- and enantiocontrol in the ensuing radical processes are inherently difficult. Here we report an enantioselective radical S–C cross-coupling between C(<i>sp</i><sup>3</sup>)–H substrates and <i>N</i>-acyl sulfenamides, combining hydrogen atom transfer with sequential stereodiscrimination and chirality transfer. Two complementary protocols under photoinduced and thermal conditions were developed to convert primary and secondary unactivated alkanes, as well as diverse α-functionalized alkanes, into alkyl radicals that engage <i>N</i>-acyl sulfenamides, delivering sulfur-stereogenic alkyl sulfilimines with high enantioselectivity. The utility of this method is demonstrated by gram-scale reactions, downstream transformations into other sulfur-based chiral architectures and late-stage functionalization of pharmaceuticals and related compounds.</p><p></p>

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Enantioselective synthesis of sulfur-stereogenic alkyl sulfilimines with C(sp3)–H-derived alkyl radicals using copper catalysis

  • 期刊论文

  • 发表日期：

    2026年5月22日

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  • Li-Wen Fan,
  • Li Qin,
  • Chen-Yu Xiao,
  • Jun-Bin Tang,
  • Hang Lv,
  • Qiao Song,
  • Fu Liu,
  • Jia-Peng Wang,
  • Yu-Shuai Zhang,
  • Dai-Lei Yuan,
  • Jun-Qian Bian,
  • Qiang-Shuai Gu,
  • Xin-Yuan Liu

摘要

Sulfur-stereogenic motifs are important in natural products, pharmaceuticals, agrochemicals and chiral ligands and catalysts, and are increasingly explored in functional materials. Direct enantioselective S-alkylation using non-prochiral C(sp3)–H bonds, particularly unactivated ones, offers an ideal atom-economical route to sulfur-stereogenic centres, yet remains highly challenging as their activation typically requires strong oxidants, and chemo- and enantiocontrol in the ensuing radical processes are inherently difficult. Here we report an enantioselective radical S–C cross-coupling between C(sp3)–H substrates and N-acyl sulfenamides, combining hydrogen atom transfer with sequential stereodiscrimination and chirality transfer. Two complementary protocols under photoinduced and thermal conditions were developed to convert primary and secondary unactivated alkanes, as well as diverse α-functionalized alkanes, into alkyl radicals that engage N-acyl sulfenamides, delivering sulfur-stereogenic alkyl sulfilimines with high enantioselectivity. The utility of this method is demonstrated by gram-scale reactions, downstream transformations into other sulfur-based chiral architectures and late-stage functionalization of pharmaceuticals and related compounds.