Concise Total Synthesis and Stereochemical Assignment of (–)-Psychotridine.

We report the first enantioselective total synthesis and stereochemical assignment of (–)-psychotridine. Application of our diazene-directed assembly of enantiomerically enriched cyclotryptamines afforded a highly convergent synthesis of the pentameric alkaloid, allowing its detailed structural assignment. Highlights of the synthesis include introduction of four quaternary stereocenters with complete stereochemical control in a single step via photoextrusion of three molecules of dinitrogen from an advanced intermediate and metal-catalyzed C–H amination in complex settings.