Total Synthesis of Strychnine

The total synthesis of the flagship Strychnos indole alkaloid, strychnine, has been accomplished. The developed synthetic sequence features a novel vinylogous 1,4‐addition, a challenging iodinium salt mediated silyl enol ether arylation, a palladium‐catalyzed Heck reaction, and a streamlined late‐stage conversion to strychnine. Furthermore, an application of asymmetric counterion‐directed catalysis (ACDC) in the context of target‐oriented organic synthesis has been rendered access to an optically active material. The synthetic sequence described herein represents the most concise entry to optically active strychnine to date. What′s your poison? An expedient total synthesis of strychnine has been accomplished through a newly developed reaction sequence involving a catalytic asymmetric counteranion‐directed vinylogous 1,4‐addition, a silyl enol ether quaternary arylation, and an intramolecular Heck reaction.