Previously, the generation of alkyl gold intermediates (B) from nucleophilic addition to inactivated alkenes was limited by the use of trigold oxo complexes (A) with arylphosphine ligands, [(Ar3PAu)3O]BF4, in the presence of amine base. In this mechanism study, we have found that the basicity of the gold complex is key to favoring alkyl gold complex formation. Kinetic and substrate studies have shown that the strongly Bronsted basic IPrAuOH also mediates alkyl gold complex formation. The observation of an intermediate gold amide complex suggests these processes are initiated by deprotonation of the nucleophile. Trigold oxo reactions in the absence of base reveal that the byproduct from the reaction of substrate with A is digold hydroxide complex, [(LAu)2OH]BF4 (C). This complex is catalytically active for urea hydroamination at room temperature to form pyrrolidine D; however, it does not catalyze the hydroalkoxylation of the alcohol substrate. Importantly, catalysis to D occurs faster than can be accounte...