Total Syntheses of (+)‐Villocarine A, (–)‐Apogeissoschizine, and (+)‐Geissoschizine

Total syntheses of geissoschizine-type monoterpenoid indole alkaloids (MTIAs) are reported. Intramolecular Pictet–Spengler cyclization was developed for the selective construction of the 3R stereocenter. First total synthesis of (+)-villocarine A was then achieved. Furthermore, the first total synthesis of highly strained (−)-apogeissoschizine was also accomplished via aza-Michael cyclization/E1cB elimination/stereoselective olefin isomerization sequence. Finally, (+)-geissoschizine, a common biosynthetic intermediate of MTIAs, was obtained from apogeissoschizine via a ring-opening reaction along with a release of ring strain.