Gold(I)/Gold(III) Catalysis that Merges Oxidative Addition and π‐Alkene Activation

Abstract Heteroarylation of alkenes with aryl iodides was efficiently achieved with a (MeDalphos)AuCl complex through Au I /Au III catalysis. The possibility to combine oxidative addition of aryl iodides and π‐activation of alkenes at gold is demonstrated for the first time. The reaction is robust and general (>30 examples including internal alkenes, 5‐, 6‐, and 7‐membered rings). It is regioselective and leads exclusively to trans addition products. The (P,N) gold complex is most efficient with electron‐rich aryl substrates, which are troublesome with alternative photoredox/oxidative approaches. In addition, it provides a very unusual switch in regioselectivity from 5‐ exo to 6‐ endo cyclization between the Z and E isomers of internal alkenols.