The unique heteroaromatic framework of the marine alkaloid violatinctamine has been assembled using a onepot Pictet-Spengler-autoxidation sequence. Control studies infer the initially formed tetrahydroisoquinoline undergoes a triplet oxygen-mediated autoxidation to the dihydroisoquinoline. Further studies led to a biomimetic synthesis and structural affirmation of the insect derived monoamine polyrhadopamine D.