A series of gold(III) complexes supported by pyridine-based bis(amidate), bis(carboxylate), and bis(iminothiolate) substituents is reported. These compounds represent rare examples of pincer-ligated gold(III) centers with multiple anionic heteroaom donors. Reactivity and electrochemical studies demonstrate the stability of these compounds and the marked difference in reduction potentials with varying ligand scaffolds.

The gold-catalyzed enantioselective hydroazidation and hydroamination reactions of allenes are presented herein. ADC gold(I) catalysts derived from BINAM were critical for achieving high levels of enantioselectivity in both transformations. The sense of enantioinduction is reversed for the two different nucleophiles, allowing access to both enantiomers of the corresponding allylic amines using the same catalyst enantiomer.

The development of a gold(I)-catalyzed sulfination of aryl boronic acids is described. This transformation proceeds through an unprecedented mechanism which exploits the reactivity of gold(I)-heteroatom bonds to form sulfinate anions. Further in situ elaboration of the sulfinate intermediates leads to the corresponding sulfones and sulfonamides, two pharmacophores routinely encountered in drug discovery.