Zhu Xinhao, Wan Kerou, Zhang Jin, Zhao Hui, He Yang, Ma Yangmin, Yang Xiufang, Szostak Michal
College of Chemistry and Chemical Engineering, Key Laboratory of Chemical Additives for China National Light Industry, Shaanxi University of Science and Technology, Xi'an 710021, China.
Shaanxi Key Laboratory of Catalytic Materials and Technology, Kaili Catalyst & New Materials Company, Ltf., Xi'an 710299, China.
Org Lett. 2023 Aug 25;25(33):6149-6154. doi: 10.1021/acs.orglett.3c02238. Epub 2023 Aug 14.
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 -Boc-thioamides that engage in ground-state destabilization of the n → π* conjugation. The ground-state destabilization of "single-atom" bioisosteric thioamides will expand the arsenal of valuable amide bond functionalization reactions.
在此，我们报道了一种极其温和的方法，通过选择性生成四面体中间体，实现硫代酰胺的直接、无过渡金属酯化反应。该方法代表了有机合成中从硫代酰胺到硫代酯转化的第一种无过渡金属方法。这种反应性是通过参与n→π*共轭基态去稳定化的-Boc-硫代酰胺实现的。“单原子”生物电子等排体硫代酰胺的基态去稳定化将扩大有价值的酰胺键官能化反应的范围。
