title: 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.
authors.affiliation: Department of Applied Chemistry, Graduate School of Engineering, Nagoya University, Nagoya, 464-8603, Japan.
authors.forename: Ayaka
authors.initials: A
authors.lastname: Yamaji
authors.affiliation: Department of Chemistry, Graduate School of Engineering Science, Osaka University, Osaka, 560-8531, Japan.
authors.forename: Hayato
authors.initials: H
authors.lastname: Tsurugi
authors.affiliation: Department of Applied Chemistry, Graduate School of Engineering, Nagoya University, Nagoya, 464-8603, Japan. miyake@apchem.nagoya-u.ac.jp.
authors.forename: Yoshihiro
authors.initials: Y
authors.lastname: Miyake
authors.affiliation: Department of Chemistry, Graduate School of Engineering Science, Osaka University, Osaka, 560-8531, Japan.
authors.forename: Kazushi
authors.initials: K
authors.lastname: Mashima
authors.affiliation: Department of Applied Chemistry, Graduate School of Engineering, Nagoya University, Nagoya, 464-8603, Japan. hshino@apchem.nagoya-u.ac.jp.
authors.forename: Hiroshi
authors.initials: H
authors.lastname: Shinokubo
keywords: antiaromaticity; chemoselectivity; porphyrinoids; reduction; tautomerism