Nature‐Inspired Stereospecific Total Synthesis of P‐(+)‐Dispegatrine and Four Other Monomeric Sarpagine Indole Alkaloids

All five: The first total synthesis of the C2-symmetric indole alkaloid 1 involved a late-stage thallium(III) acetate-mediated intermolecular oxidative coupling to construct the C9C9′ bond with complete regio- and stereocontrol. The formation of a single atropodiastereomer in this critical step arises from internal asymmetric induction. The first total synthesis of four other monomeric sarpagine indole alkaloids is also described.