Rhodium-catalyzed denitrogenative gem -difunctionalization of pyridotriazoles with thioesters: formal carbene insertion into C(O)-S bonds.

A formal carbene insertion into C(O)-S bonds to access α-quaternary pyridines was achieved via a rhodium(II)-catalyzed in situ formation of sulfonium ylides from pyridotriazoles with thioesters followed by acyl group migration. This protocol has enabled an efficient denitrogenative gem -acylthiolation of pyridotriazoles to incorporate an acyl, pyridyl, and sulfur-substituted quaternary carbon center with high selectivity, broad substrate scope, and good functional group tolerance.