A four-step synthesis of (−)-lentiginosine and its epimers isdescribed starting from 2-bromopyridine. The key stepconsisted of a quaternarization of a fully unprotectedpyridinium-polyol unit using Mitsunobu methodology. Subsequent PtO2-catalyzed diastereoselective hydrogenation ofthe pyridinium ring proceeded smoothly and led to theexpected dihydroxyindolizidines with excellent yields. Thisstereochemically flexible strategy has been illustrated by theconcise total synthesis of non-natural products derivativessuch as (−)-lentiginosine and its stereoisomers in high yields.