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

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.