Synthesis of Polysubstituted Enamides by Hydrogen Atom Transfer Alkene Isomerization Using Dual Cobalt/Photoredox Catalysis

M‐HAT isomerization is a highly reliable method to access thermodynamically stable alkenes with high functional group tolerance. However, synthesis of heteroatom‐substituted alkenes by M‐HAT isomerization reaction is still underdeveloped. Herein, we report an enamide synthesis using M‐HAT via a combination of cobalt and photoredox catalysis. This method tolerates a variety of functional groups including haloarenes, heteroarenes, free hydroxy groups, non‐protected indoles, and drug derivatives. Furthermore, this method can isomerize styrene derivatives in good yield and E/Z selectivity. Synthesis of polysubstituted enamides via metal‐catalyzed hydrogen atom transfer by merger of cobalt/photoredox catalysis was achieved. The judicious choice of Co(3‐tert‐butyl‐5‐CF3‐salophen) and Co(3,5‐di‐tert‐butylsalophen) enabled access to polysubstituted enamides. The method tolerated haloarenes, heteroarenes, free hydroxy groups, non‐protected indoles, and drug‐like molecules. Furthermore, this method can isomerize styrene derivatives in good yield and E/Z selectivity.