A concise enantioselective total synthesis of the cardiovascular agent (-)-ajmalicine and an approach toward the synthesis of (+)-19-epiajmalicine are described. The key step of the (-)-ajmalicine synthesis is a carboxylate-terminated N-acyliminium ion biscyclization (74 --> 67), which assembles the D and E rings of this heteroyohimbine alkaloid in one step. A related carboxylate-terminated iminium ion biscyclization (28 --> 29) is the central step in the approach to (+)-epiajmalicine.