Total Synthesis of (−)-Stemonine

An enantioselective total synthesis of (−)-stemonine (1) is reported via a convergent assembly of the acyclic precursor 2. Key transformations include a Staudinger−aza-Wittig reaction to form the central perhydroazepine ring system and an iodine-induced tandem cyclization to construct the pyrrolidino-butyrolactone framework.