Enantiopure tert-butanesulfinamide can be prepared by enantioselective oxidation of inexpensive di-tert-butyl disulfide to the thiosulfinate followed by disulfide bond cleavage by lithium amide. In the original scope the chiral ligand used together with vanadyl acetylacetonate was prepared by condensing an optically pure chiral aminoindanol with 3,5-di-tert-butyl salicylaldehyde.