Starting from D-xylose, enantioselective syntheses of 1 and 2, the proposed structures for radicamines A and B, were accomplished. Both 1H and 13C NMR spectra of 1 and 2 were identical with those of the natural products, but the optical rotation measurements identified that 1 and 2 were actually the enantiomers of the natural radicamines A and B, respectively.