Divergent Reactivity of E / Z ‐Azobenzene‐Based Phosphine‐Gold Catalysts: Toward an ON‐ON Catalytic Photoswitch Process

Abstract This work discloses a strategy for the implementation of ON‐ON organometallic catalytic processes using photoresponsive phosphine ligands. The approach leverages on the regiodivergent reactivity of mono‐ and bimetallic gold complexes that results from π‐ vs σ,π‐activations of alkynyl‐substituted urea substrates, for the selective formation of either dihydroquinazolinone or indole‐carboxamide products, via intramolecular hydroamidation.