Scholarlink

<p>Delocalized radical systems present a challenging yet appealing ground to test the control of multiple selectivity in organic synthesis. Despite some recent advances, the issue of regioselectivity in delocalized radical systems has largely centred on allylic radicals. To explore larger delocalized radical systems, we report the catalytic generation of extensively delocalized 4-vinylphenoxyl radicals and their involvement as key intermediates in regioselective radical C–N bond formation. Guided by the mechanistic principles of metalloradical catalysis, we develop a Co(II)-based enantioselective radical system for dearomative 1,7-conjugate amination of readily available 4-vinylphenols with aryl azides. This can afford valuable chiral α-tertiary amino acid derivatives in high yields with excellent enantioselectivities for the newly created tetrasubstituted stereocentres. Unlike previous systems, this amination involves hydrogen-atom abstraction from O–H bonds. As demonstrated with 1,6-conjugate addition with various nucleophiles, the resulting α-tertiary amino acid derivatives, which bear additional <i>para</i>-quinone methide functionality, may find useful synthetic applications.</p><p></p>

错误：搜索内容不能为空，请输入英文关键词
错误：关键词超出字数限制，请精简
高级检索

Enantioselective radical dearomative conjugate amination enabled by Co(II)-based metalloradical catalysis

  • 期刊论文

  • 发表日期：

    2025年10月6日

查看全文
  • Pan Xu,
  • Duo-Sheng Wang,
  • Zhenyu Zhu,
  • X. Peter Zhang

摘要

Delocalized radical systems present a challenging yet appealing ground to test the control of multiple selectivity in organic synthesis. Despite some recent advances, the issue of regioselectivity in delocalized radical systems has largely centred on allylic radicals. To explore larger delocalized radical systems, we report the catalytic generation of extensively delocalized 4-vinylphenoxyl radicals and their involvement as key intermediates in regioselective radical C–N bond formation. Guided by the mechanistic principles of metalloradical catalysis, we develop a Co(II)-based enantioselective radical system for dearomative 1,7-conjugate amination of readily available 4-vinylphenols with aryl azides. This can afford valuable chiral α-tertiary amino acid derivatives in high yields with excellent enantioselectivities for the newly created tetrasubstituted stereocentres. Unlike previous systems, this amination involves hydrogen-atom abstraction from O–H bonds. As demonstrated with 1,6-conjugate addition with various nucleophiles, the resulting α-tertiary amino acid derivatives, which bear additional para-quinone methide functionality, may find useful synthetic applications.