Scholarlink

<p>Due to the universality of arylamine and arylazide building blocks in pharmaceuticals, natural products and functional materials, the formation of aryl C-N bonds from readily available materials appears to be highly appealing, especially for the exclusive regioselective C-H amination. Despite substantial advancements in the synthesis of aryl C-N bonds, achieving a general, efficient, and <i>para</i>-selective C-H amination under mild conditions remains a significant challenge. Here we showcase a fluorosulfuryl imidazolium triflate-mediated <i>para-</i>selective C-H amination of <i>N-</i>arylhydroxylamines employing primary and secondary amines, diphenylmethanimine and azides as nitrogen source, affording structurally diverse 1,4-diaminoarenes or <i>para</i>-azidoanilides in the absence of oxidants and transition-metal catalysts. This effective protocol exhibits exclusive <i>para</i>-selectivity and good functional group tolerance for both <i>N</i>-arylhydroxylamines and <i>N</i>-nucleophiles (&gt;90 examples). DFT calculations have been performed to elucidate the high chemoselectivity observed amidst multiple nucleophilic and electrophilic species.</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

Metal-free para-selective C-H amination and azidation of N-arylhydroxylamines

  • 期刊论文

  • 出版模式：

    开放获取

  • 发表日期：

    2025年9月25日

查看全文
  • Yaru Bai,
  • Hui-Mei Jiang,
  • Wenbo Xu,
  • Li-Ping Xu,
  • Hongyin Gao

摘要

Due to the universality of arylamine and arylazide building blocks in pharmaceuticals, natural products and functional materials, the formation of aryl C-N bonds from readily available materials appears to be highly appealing, especially for the exclusive regioselective C-H amination. Despite substantial advancements in the synthesis of aryl C-N bonds, achieving a general, efficient, and para-selective C-H amination under mild conditions remains a significant challenge. Here we showcase a fluorosulfuryl imidazolium triflate-mediated para-selective C-H amination of N-arylhydroxylamines employing primary and secondary amines, diphenylmethanimine and azides as nitrogen source, affording structurally diverse 1,4-diaminoarenes or para-azidoanilides in the absence of oxidants and transition-metal catalysts. This effective protocol exhibits exclusive para-selectivity and good functional group tolerance for both N-arylhydroxylamines and N-nucleophiles (>90 examples). DFT calculations have been performed to elucidate the high chemoselectivity observed amidst multiple nucleophilic and electrophilic species.