Abstract: | Dihydroxyverbacine ( 10 ), a precursor for oxidative phenol coupling, was obtained via (±)‐buchnerine ( 14 ), whose synthesis is described. The oxidizing system hemin (ferriprotoporphyrin IX chloride)/H2O2 promoted intramolecular coupling of 10 to give the alkaloids aphelandrine ( 1 ), orantine ( 2 ), and chaenorpine ( 7 ). The alkaloids were identified by on‐line coupled HPLC and atmospheric‐pressure chemical‐ionization (APCI) mass spectrometry. |