A new structural phenanthroindolizidine, 2,3,6,7-tetramethoxyphenanthro[9,10,3',4']indolizidine, has beensynthesized efficiently from pyrrole. An important feature of this synthesis is that intramolecular oxidativecoupling and rearrangement of 6,7-bis(3,4-dimethoxyphenyl)-8-methoxy-1,2,3-trihydroindolizin-5-one byusing VOF
3 and TFA have been achieved in one pot.