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

14 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

All Science Journal Classification (ASJC) codes

  • Catalysis
  • Chemistry(all)

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