Photoinduced Nickel Catalysis for the Z ‐Selective Monoisomerization of Terminal Alkenes

The isomerization of readily available terminal alkenes is a valuable transformation for the synthesis of internal alkenes; however, competing overisomerization and the formation of E / Z isomers are inevitable issues. Herein, we report the Z ‐selective monoisomerization of terminal alkenes at ambient temperature using a combination of NiI 2 , 1,3‐bis(dicyclohexylphosphino)propane, and 2,4,5,6‐tetrakis(9H‐carbazol‐9‐yl)isophthalonitrile (4CzIPN) under visible‐light irradiation. Various homoallyl arenes and simple terminal alkenes underwent the selective isomerization to 2‐alkenes with good Z ‐selectivity. The reaction is proposed to proceed via a Ni–hydride pathway, and experimental studies revealed that photoinduced processes generate the active catalytic species.