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 journalArticlepeer-review

    20 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)

    Fingerprint

    Dive into the research topics of 'Rational Synthesis of Antiaromatic 5,15-Dioxaporphyrin and Oxidation into β,β-Linked Dimers'. Together they form a unique fingerprint.

    Cite this