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

Abstract

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.