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

Research output: Contribution to journalArticle

8 Citations (Scopus)

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 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.

Original languageEnglish
Pages (from-to)9728-9733
Number of pages6
JournalAngewandte Chemie - International Edition
Volume57
Issue number31
DOIs
Publication statusPublished - Jul 26 2018

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

All Science Journal Classification (ASJC) codes

  • Catalysis
  • Chemistry(all)

Cite this

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.

In: Angewandte Chemie - International Edition, Vol. 57, No. 31, 26.07.2018, p. 9728-9733.

Research output: Contribution to journalArticle

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. In: Angewandte Chemie - International Edition. 2018 ; Vol. 57, No. 31. pp. 9728-9733.
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