Copper-catalyzed, N-directed remote C(sp3)–H azidation and thiocyanation

Abstract

An efficient and general method for the catalytic installation of azido and thiocyanato groups via remote C(sp³)–H activation is described. The copper-catalyzed reaction proceeds through a cascade of single-electron transfer, favorable 1,5-hydrogen atom transfer, and C–N/C–S cross-coupling, thus providing the distal azido and thiocyanato alkylamines. This reaction could be applicable to primary, secondary, tertiary, and benzylic C(sp³)–H functionalization, as well as demonstrating excellent site-selectivity and functional-group compatibility.