The readily available enantiomers of bornane(10,2)sultam serve as efficient, versatile and practical chiral auxiliaries. A selection of highly χ-face-selective reactions of their N-enoyl derivatives (Diels-Alder additions, dihydroxylations, 1,4-additions) as well as of their 0-metalated N,O-ketene acetals (aldolizations, alkylations, brominations, "aminations") are described. Applications to the syntheses of natural products and, particularly, of enantiomerically pure α-amino acids demonstrate their preparative potential.