Abstract (+)-(S)-Streptenol A is synthesized by coupling a 1, 3-dithiane with an optically pure epoxide. The absolute configuration of (+)-(S)-streptenol A is thereby correlated with that of (S)-malic acid. Stereoselective reduction of an oxime that could easily be prepared from streptenol A gave the (3S, 5R)-and (3S, 5S)-aminostreptenols, and after cyclization, configurationally pure 2, 4-functionalized piperidine alkaloids.