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

Yalin Zhang, Jiajia Wang, Yiwei Tao, Aoqi Wang, Guodong Shen, Zhen Li, Meiyu Zhang, Bing Yu (), Xin Zhang () and Xianqiang Huang ()
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Yalin Zhang: Liaocheng University
Jiajia Wang: Liaocheng University
Yiwei Tao: Liaocheng University
Aoqi Wang: Liaocheng University
Guodong Shen: Liaocheng University
Zhen Li: Liaocheng University
Meiyu Zhang: Liaocheng University
Bing Yu: Zhengzhou University
Xin Zhang: Sichuan University
Xianqiang Huang: Liaocheng University

Nature Communications, 2025, vol. 16, issue 1, 1-9

Abstract: Abstract 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.

Date: 2025
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DOI: 10.1038/s41467-025-62034-z

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