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

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