Cu-Catalyzed Oxidative Thioesterification of Aroylhydrazides with Disulfides

An alternative thioesterification reaction via copper-catalyzed oxidative coupling of readily available aroylhydrazides with disulfides is developed, in which oxidative expulsion of N-2 overcomes the activation barrier between the carboxylic acid derivatives and the products. The reaction produces various thioesters in good to excellent yields with good functional group tolerance. In the reaction, stable and easily available aroylhydrazides are used as acyl sources and the relatively odorless disulfides are used as S sources. Mechanistic investigations demonstrate that the reaction of copper salt and oxidant (NH4)(2)S2O8 allows for achievement of tandem processes, including deprotonation, free-radical-mediated denitrogenation, and C-S bond formation.

Automated summary

The alternative thioesterification reaction developed in this study utilizes readily available aroylhydrazides and disulfides, producing various thioesters in good to excellent yields with good functional group tolerance. The reaction mechanism involves tandem processes including deprotonation, free-radical-mediated denitrogenation, and C-S bond formation facilitated by the reaction of copper salt and oxidant (NH4)(2)S2O8.