We describe a AuI 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” AuI/AuIII 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.

l-Tyrosine provides a precursor for a practical synthesis of the unstable primary metabolite l-arogenate and some stabilised arogenate analogues.

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 oxidantfree" Au I /Au III catalyzed 1,2-oxyarylations of ethylene and propylene. These demanding yet powerful processes establish these commodity chemicals as nucleophilicelectrophilic building blocks in catalytic reaction design.