A new alkaloid from Voacanga africana was identified as the hydroxyindolenine derivative (6) of voacangine, and its structure was proven by synthesis. A rearrangement product of 6, the pseudoindoxyl 9, was also encountered and characterized. Two additional new alkaloids, the hydroxyindolenine (7) and pseudoindoxyl (10) derivatives of voacristine were synthesized. Mass spectra of all compounds are presented and interpreted. © 1968.