Isoandrosterone (V) is converted by an eighteen-stage process to a mixture of tigogenin (LXIII) and neotigogenin (LXIV). Each of these steroidal sapogenins is obtained in the pure state and is identitied with an authentic sample. The synthesis leads to other steroidal sapogenins (smilagenin, gitogenin, diosgenin, chlorogenin, hecogenin) as well as to certain steroidal alkaloids (tomatidine, solasodine).