TY - JOUR
T1 - Rational Synthesis of Antiaromatic 5,15-Dioxaporphyrin and Oxidation into β,β-Linked Dimers
AU - Nishiyama, Akihide
AU - Fukuda, Masaya
AU - Mori, Shigeki
AU - Furukawa, Ko
AU - Fliegl, Heike
AU - Furuta, Hiroyuki
AU - Shimizu, Soji
N1 - Funding Information:
This work was supported by Grants-in-Aid for Young Scientists A (JSPS KAKENHI Grant Number JP26708003) and Scientific Research on Innovative Area, “p-System Figuration: Control of Electron and Structural Dynamism for Innovative Functions (No. 2601)” (JSPS KAKENHI Grant Number JP15H01001). H.F. thanks the Norwegian Research Council through the CoE Hylleraas Centre for Quantum Molecular Sciences (Grant Nos. 262695 and 231571/ F20) for support. This work has received support from the Norwegian Supercomputing Program (NOTUR) through a grant of computer time (Grant No. NN4654K).
Publisher Copyright:
© 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
PY - 2018/7/26
Y1 - 2018/7/26
N2 - 5,15-Dioxaporphyrin was synthesized for the first time by a nucleophilic aromatic substitution reaction of a nickel bis(α,α′-dibromodipyrrin) complex with benzaldoxime, followed by an intramolecular annulation of the α-hydroxy-substituted intermediate. This unprecedented molecule is a 20π-electron antiaromatic system, in terms of Hückel's rule of aromaticity, because lone pair electrons of oxygen atoms are incorporated into the 18π-electron conjugated system of the porphyrin. A theoretical analysis based on the gauge-including magnetically induced current method confirmed its antiaromaticity and a dominant inner ring pathway for the ring current. The unique reactivity of 5,15-dioxaporphyrin forming a β,β-linked dimer upon oxidation was also revealed.
AB - 5,15-Dioxaporphyrin was synthesized for the first time by a nucleophilic aromatic substitution reaction of a nickel bis(α,α′-dibromodipyrrin) complex with benzaldoxime, followed by an intramolecular annulation of the α-hydroxy-substituted intermediate. This unprecedented molecule is a 20π-electron antiaromatic system, in terms of Hückel's rule of aromaticity, because lone pair electrons of oxygen atoms are incorporated into the 18π-electron conjugated system of the porphyrin. A theoretical analysis based on the gauge-including magnetically induced current method confirmed its antiaromaticity and a dominant inner ring pathway for the ring current. The unique reactivity of 5,15-dioxaporphyrin forming a β,β-linked dimer upon oxidation was also revealed.
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U2 - 10.1002/anie.201804648
DO - 10.1002/anie.201804648
M3 - Article
C2 - 29901249
AN - SCOPUS:85050488217
SN - 1433-7851
VL - 57
SP - 9728
EP - 9733
JO - Angewandte Chemie - International Edition
JF - Angewandte Chemie - International Edition
IS - 31
ER -