Scandium-catalyzed chemoselective carbene insertion into N–H over S–H: access to o-alkylamine-diaryl disulfides

Abstract

Herein, we report a scandium-catalyzed chemoselective carbene insertion into a N–H bond over a S–H bond with disulfide formation. This reaction represents the first example of the synthesis of o-alkylamine-diaryl disulfides through the N-alkylation of o-aminobenzenethiol, while also undergoing oxidative coupling to form a S–S bond. Control experiments explain the chemo-selectivity of this rare-earth-metal Lewis acid-induced catalysis by a carbene outer-sphere nucleophilic addition mechanism. This method holds tremendous potential as a valuable tool for functionalizing advanced-synthetic-intermediates, offering numerous applications in medicinal and materials chemistry.