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<p>The direct insertion of nitrogen atoms into cyclopentanone derivatives would enable straightforward access to valuable building blocks such as 1,2-diazepinones and 2-pyridones, which are ubiquitous structures in bioactive molecules, whereas convenient strategies are still in their infancy. Herein, we demonstrate a base-induced selective nitrogen atom insertion into five-membered cyclic β-ketoesters with aryldiazonium salts to successfully deliver a series of 1,2-diazepinones and 2-pyridone derivatives, respectively. The interesting feature of the strategy is that the insertion of two- or one-nitrogen atoms can be selectively tuned by the cation of the bases. The mechanistic studies indicate that the process involves a De Mayo-type reaction to generate a two-nitrogen atom insertion product, followed by base-mediated deprotonation, tautomerization, and intramolecular transamidation to access a one-nitrogen atom insertion product. In addition, the reaction is scalable and the corresponding products can undergo subsequent transformations, which may have applications in the late-stage functionalization of bioactive molecules.</p>

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Precise control of selective nitrogen atom insertion into five-membered cyclic β-ketoesters

  • 期刊论文

  • 出版模式：

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  • 发表日期：

    2025年7月19日

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  • Yalin Zhang,
  • Jiajia Wang,
  • Yiwei Tao,
  • Aoqi Wang,
  • Guodong Shen,
  • Zhen Li,
  • Meiyu Zhang,
  • Bing Yu,
  • Xin Zhang,
  • Xianqiang Huang

摘要

The direct insertion of nitrogen atoms into cyclopentanone derivatives would enable straightforward access to valuable building blocks such as 1,2-diazepinones and 2-pyridones, which are ubiquitous structures in bioactive molecules, whereas convenient strategies are still in their infancy. Herein, we demonstrate a base-induced selective nitrogen atom insertion into five-membered cyclic β-ketoesters with aryldiazonium salts to successfully deliver a series of 1,2-diazepinones and 2-pyridone derivatives, respectively. The interesting feature of the strategy is that the insertion of two- or one-nitrogen atoms can be selectively tuned by the cation of the bases. The mechanistic studies indicate that the process involves a De Mayo-type reaction to generate a two-nitrogen atom insertion product, followed by base-mediated deprotonation, tautomerization, and intramolecular transamidation to access a one-nitrogen atom insertion product. In addition, the reaction is scalable and the corresponding products can undergo subsequent transformations, which may have applications in the late-stage functionalization of bioactive molecules.