Treatment of multisubstituted NH-enesulfinamides with tosyl isocyanate (TsNCO) at room temperature results in the formation of α-tosylcarbamoyloxy N-sulfenyl ketimines with high enantioselectivity. This process is believed to proceed via a vinylogous aza-Pummerer-type reaction pathway in which the sulfinyl oxygen atom in the enesulfinamides undergoes nucleophilic attack on tosyl isocyanate, triggering the subsequent transformations that enable the transfer of chirality from sulfur to carbon.