Phosphine-catalyzed formation of carbon-sulfur bonds: catalytic asymmetric synthesis of gamma-thioesters.

A method for catalytic asymmetric gamma sulfenylation of carbonyl compounds has been developed. In the presence of an appropriate catalyst, thiols not only add to the gamma position of allenoates, overcoming their propensity to add to the beta position in the absence of a catalyst, but do so with very good enantioselectivity. Sulfur nucleophiles are now added to the three families of nucleophiles (carbon, nitrogen, and oxygen) that had earlier been shown to participate in catalyzed gamma additions. The phosphine catalyst of choice, TangPhos, had previously only been employed as a chiral ligand for transition metals, not as an efficient enantioselective nucleophilic catalyst.