The straightforward enantioselective construction of the hydroquinoline ring system from 1,5-polycarbonyl derivatives, using (R)-phenyglycinol as a chiral latent form of ammonia, is reported. The process mimics the key steps believed to occur in nature in the biosynthesis of amphibian decahydroquinoline alkaloids. Diastereodivergent routes to enantiopure cis-2,5-disubstituted decahydroquinolines, including the alkaloid pumiliotoxin C (cis-195A), are developed.