Formation of hydroxyindolenine derivatives by photoinduced oxidation by singlet oxygen of intermediate 3 beta -cyanocatharanthine (3) allows us to synthesize under mild conditions new alkaloids derivatives, 3 beta -cyano-7 beta -hydroxyindolenine-catharanthine (5), 3 beta -cyano-7 beta -hydroxyindolinecatharanthine (6) and 7 beta -hydroxy-indolenine-catharanthine (7), bearing protected indole moities.