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

Xinhao Zhu; Kerou Wan; Jin Zhang; Hui Zhao; Yang He; Yangmin Ma; Xiufang Yang; Michal Szostak

doi:10.1021/acs.orglett.3c02238

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

Org Lett. 2023 Aug 25;25(33):6149-6154. doi: 10.1021/acs.orglett.3c02238. Epub 2023 Aug 14.

Authors

Xinhao Zhu¹, Kerou Wan², Jin Zhang¹, Hui Zhao¹, Yang He¹, Yangmin Ma¹, Xiufang Yang¹, Michal Szostak³

Affiliations

¹ 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.
² Shaanxi Key Laboratory of Catalytic Materials and Technology, Kaili Catalyst & New Materials Company, Ltf., Xi'an 710299, China.
³ Department of Chemistry, Rutgers University, 73 Warren Street, Newark, New Jersey 07102, United States.

PMID: 37578346
DOI: 10.1021/acs.orglett.3c02238

Abstract

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-Boc₂-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.