Esterification of Thioamides via Selective N–C(S) Cleavage under Mild Conditions

作者：Xinhao Zhu, Kerou Wan, Jin Zhang, Hui Zhao, Yang He, Yangmin Ma, Xiufang Yang, Michal Szostak · 发表于：Organic Letters · 年份：2023 · DOI：10.1021/acs.orglett.3c02238 · 被引用次数：8 · 研究领域：Synthesis and Reactivity of Sulfur-Containing Compounds、Synthesis of heterocyclic compounds、Advanced Synthetic Organic Chemistry

Herein, we report an exceedingly mild method for the direct, transition-metal-free esterification of thioamides through the selective generation of tetrahedral intermediates. The method represents the first transition-metal-free approach to the thioamide to thionoester transformation in organic synthesis. This reactivity has been accomplished through N,N -Boc 2 -thioamides that engage in ground-state destabilization of the n N → π* C═S conjugation. The ground-state destabilization of “single-atom” bioisosteric thioamides will expand the arsenal of valuable amide bond functionalization reactions.