A Hemilabile NHC‐Gold Complex and its Application to the Redox Neutral 1,2‐Oxyarylation of Feedstock Alkenes

Abstract We describe a Au I complex of a hemi‐labile (C^N) N‐heterocyclic carbene ligand that is able to mediate oxidative addition of aryl iodides. Detailed computational and experimental investigations have been undertaken to verify and rationalize the oxidative addition process. Application of this initiation mode has resulted in the first examples of “exogenous oxidant‐free” Au I /Au III catalyzed 1,2‐oxyarylations of ethylene and propylene. These demanding yet powerful processes establish these commodity chemicals as nucleophilic‐electrophilic building blocks in catalytic reaction design.