An efficient enantioselective synthesis of (−)-cytoxazone (1) and (+)-epi-cytoxazone (2) using proline-catalyzed asymmetric α-amino-oxylation of aldehydes followed by Rh-catalyzed diastereoselective oxidative C–H amination as the key steps is described. syn or anti 1,2-aminoalcohols were obtained by Rh-catalyzed intramolecular amidation of the C–H bonds of carbamates or sulfamate esters with good to excellent diastereoselectivity.