Chemo‐ and Regioselective Reduction of 5,15‐Diazaporphyrins Providing Antiaromatic Azaporphyrinoids

Reagent‐controlled chemo‐ and regioselective reduction of 5,15‐diazaporphyrins has been developed. The selective reduction of carbon–carbon double bonds of diazaporphyrins provides 18 π aromatic isobacteriochlorin‐type products, whereas the reduction of carbon–nitrogen double bonds leads to selective formation of 20 π N , N ′‐dihydrodiazaporphyrins in excellent yields. The distinct antiaromatic character of N , N ′‐dihydrodiazaporphyrins has been revealed. The free‐base N , N ′‐dihydrodiazaporphyrin exhibits slower inner NH tautomerism than that in the corresponding 18 π porphyrins.