Anthracene Bisurea as a Supramolecular Chloride Receptor for Additive‐Free, Broad‐Scope Gold(I) Catalysis

Gold catalysis provides access to a remarkable array of complex carbon scaffolds, but the use of silver salts to activate gold(I) chloride precatalysts can be problematic due to Ag(I) light sensitivity, hygroscopicity, redox activity, and interference with the desired catalysis. Although H-bond donors are a promising alternative to silver salts, they still suffer from much lower activity and narrower applicability, as Au-Cl cleavage remains rate limiting. To address these limitations, we have rationally designed a self-activating phosphine Au(I) chloride complex that incorporates a supramolecular chloride receptor in the form of an anthracene bisurea quintuple H-bond donor. In the absence of any additive, this complex promotes multiple intra- and intermolecular reactions, with a catalytic activity rivalling traditional inorganic chloride scavengers. Mechanistic studies for the model reaction show that the exceptional chloride binding ability of the anthracene bisurea unlocks access to a zwitterionic catalyst resting state where the Au─Cl bond has been cleaved, thus significantly reducing barriers for catalysis. The principles uncovered in this work show how supramolecular anion recognition moieties impact catalyst speciation and enhance performance, enabling for the first time H-bond donors to compete with inorganic chloride scavengers in terms of activity and generality.