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Chemo‐ and Regioselective Reduction of 5,15‐Diazaporphyrins Providing Antiaromatic Azaporphyrinoids
Author(s) -
Yamaji Ayaka,
Tsurugi Hayato,
Miyake Yoshihiro,
Mashima Kazushi,
Shinokubo Hiroshi
Publication year - 2016
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201600066
Subject(s) - antiaromaticity , regioselectivity , double bond , reagent , chemistry , tautomer , character (mathematics) , reduction (mathematics) , nitrogen , carbon fibers , stereochemistry , medicinal chemistry , organic chemistry , aromaticity , materials science , molecule , catalysis , mathematics , geometry , composite number , composite material
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.