Distal heteroaryl migration of alkenyl alcohols initiated by a metal-hydride hydrogen atom transfer (MHAT) is described. The remote migration strategy provided access to heteroaryl-containing ketones at remote positions that are inaccessible through conventional MHAT 1,2-migration pathways. Furthermore, we successfully synthesized deuterium-labeled heteroaryl-containing ketones via site-selective mono-deuteration.

Abstract

A structural isomerization of alkenyl alcohols via 1,4- or 1,5-heteroaryl migration initiated by metal-hydride hydrogen atom transfer (MHAT) under cobalt/photoredox dual catalysis is described. The remote migration method provided various heteroaryl-containing ketones inaccessible through conventional MHAT 1,2-migration pathways. The cobalt/photoredox catalysis was further applied to the synthesis of deuterium-labeled heteroaryl-containing ketones.