Exploring theElectronic and Steric Effects of Hemilabile(P^N) Ligands in Redox Gold Catalysis: Application to the Cross-CouplingReaction of Aliphatic Amines with Aryl Iodides

Herein, we report 17 new (P^N) ligands for redox gold catalysis, featuring various substituents at −C4, −C5, and −C6 of the aryl ring and nitrogen handle. Rate kinetics experiments revealed that electron-rich substituents at −C4 and −C5 positions of the aryl ring enhanced the rate of oxidative addition of Au(I) with C(sp²)–Br bonds compared to electron-poor substituents. Further, we report an unprecedented gold-catalyzed arylation of aliphatic amines using an electronically rich ligand (<b>L6</b>) with an −OMe group at the −C5 position.