Synthesis of New Chiral Amines with a Cyclic 1,2-Diacetal Skeleton Derived from (2R, 3R)-(+)-Tartaric Acid

Abstract: The syntheses of new chiral cyclic 1,2-diacetals from (2R, 3R)-( )-tartaric acidare described. C₂-symmetrical diamines were prepared via direct amidation of the tartrate orfrom the corresponding bismesylate via reaction with sodium azide. For C1-symmetricalcompounds, the Appel reaction was used to form the key intermediate, amonochlorocarbinol, from the diol. Some of the new chiral compounds, produced in good tohigh yields, may be potentially useful as asymmetric organocatalysts or as nitrogen andsulfur chelating ligands for asymmetric metal catalyzed reactions. Thus, a bis-N-methyl-methanamine derivative, used in substoichiometric amounts, was found to catalyze theenantioselective addition of cyclohexanone to (E)-β-nitrostyrene with highdiastereoselectivity (syn / anti = 92:8), albeit giving moderate optical purity (syn: 30 %).