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

By: Sun, Haoyany ; Pan, Junhong ; Zhao, Wenying ; Zhou, Tong ; Song, Xizhong ; Lin, Jun ; Jin, Yi

Chemical Communications

DOI：https://doi.org/10.1039/d4cc00557k

Published：2024-04-02

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.