Distal Heteroaryl Ipso‐Migration of Unactivated Alkenes via Cobalt/Photoredox‐Catalyzed Hydrogen/Deuterium Atom Transfer

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.