Rational Synthesis of Antiaromatic 5,15-Dioxaporphyrin and Oxidation into β,β-Linked Dimers

Akihide Nishiyama, Masaya Fukuda, Shigeki Mori, Ko Furukawa, Heike Fliegl, Hiroyuki Furuta, Soji Shimizu

研究成果: ジャーナルへの寄稿記事

抄録

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.

元の言語英語
ページ(範囲)9728-9733
ページ数6
ジャーナルAngewandte Chemie - International Edition
57
発行部数31
DOI
出版物ステータス出版済み - 7 26 2018

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Dimers
Oxidation
Electrons
Porphyrins
Induced currents
Nickel
Gages
Substitution reactions
Oxygen
Atoms
Molecules

これを引用

Rational Synthesis of Antiaromatic 5,15-Dioxaporphyrin and Oxidation into β,β-Linked Dimers. / Nishiyama, Akihide; Fukuda, Masaya; Mori, Shigeki; Furukawa, Ko; Fliegl, Heike; Furuta, Hiroyuki; Shimizu, Soji.

:: Angewandte Chemie - International Edition, 巻 57, 番号 31, 26.07.2018, p. 9728-9733.

研究成果: ジャーナルへの寄稿記事

Nishiyama, Akihide ; Fukuda, Masaya ; Mori, Shigeki ; Furukawa, Ko ; Fliegl, Heike ; Furuta, Hiroyuki ; Shimizu, Soji. / Rational Synthesis of Antiaromatic 5,15-Dioxaporphyrin and Oxidation into β,β-Linked Dimers. :: Angewandte Chemie - International Edition. 2018 ; 巻 57, 番号 31. pp. 9728-9733.
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abstract = "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 H{\"u}ckel'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.",
author = "Akihide Nishiyama and Masaya Fukuda and Shigeki Mori and Ko Furukawa and Heike Fliegl and Hiroyuki Furuta and Soji Shimizu",
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AU - Fukuda, Masaya

AU - Mori, Shigeki

AU - Furukawa, Ko

AU - Fliegl, Heike

AU - Furuta, Hiroyuki

AU - Shimizu, Soji

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