Polyneuridine aldehyde is a key intermediate in the biosynthetic routes of monoterpene indole alkaloids family of natural products. The molecule is the first biosynthetic member of the sarpagan-type alkaloids and is an entry to the ajmalan-type and alstophyllan-type alkaloids. Complementary to the recent description of polyneuridine aldehyde, its reactivity was studied. Retro-biomimetic formation of corynan-type alkaloids (e.g., geissoschizine) and the biomimetic formation of quebrachidine, the first biosynthetic parent of the ajamalan-type alkaloids, were performed. In addition, an unusual intramolecular carbonyl-ene-reaction involving the indole nucleus delivered an original polycyclic scaffold.