In summary, we have developed the first transition metalcatalyzed desymmetrization of SIA heterocycles via a Tsuji-Trost asymmetric alkylation. The optimal ligand and solvent were identified using high throughput screening. The catalyst and ligand are commercially available, and the desymmetrization is run under mild reaction conditions. The use of a variety electrophiles and heterocyclic SIAs lead to highly enantiomerically enriched products in high yields. The Trost stereochemical model accurately rationalizes the observed selectivity. Finally, the products obtained following desymmetrization are amenable to late-stage functionalization and can be used to synthesize a new class of tricyclic SIAs possessing an enantioenriched stereogenic sulfur centers.