Retro-Diels-Alder approach to the synthesis of π-expanded azuliporphyrins and their porphyrinoid aromaticity

Tetsuo Okujima, Tasuku Kikkawa, Haruyuki Nakano, Hiroshi Kubota, Nobumasa Fukugami, Noboru Ono, Hiroko Yamada, Hidemitsu Uno

Research output: Contribution to journalArticle

16 Citations (Scopus)

Abstract

Bicyclo[2.2.2]octadiene (BCOD) fused azuliporphyrins were synthesized by 3+1 porphyrin synthesis of azulitripyrranes with diformylpyrroles. Subsequent retro-Diels-Alder reaction of the BCOD-fused azuliporphyrins afforded azulibenzo-, azulidibenzo-, and azulitribenzoporphyrins 1-5. NMR and UV/Vis spectra, as well as nucleus-independent chemical shift (NICS) calculations revealed that 1-5 and their diprotonated dications exhibit relatively low porphyrinoid aromaticity, which was dependent on the position and number of fused benzene rings present. Porphyrins: A series of azulibenzoporphyrins were synthesized based on 3+1 porphyrin synthesis and retro-Diels-Alder reaction of bicyclo[2.2.2]octadiene-fused precursors (see scheme). UV/Vis spectra and NICS calculations revealed that their diprotonated dications exhibited a low porphyrinoid aromaticity from the porphyrinlike π circuit, which was dependent on the position and number of fused benzene rings.

Original languageEnglish
Pages (from-to)12854-12863
Number of pages10
JournalChemistry - A European Journal
Volume18
Issue number40
DOIs
Publication statusPublished - Oct 1 2012

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Porphyrins
Chemical shift
Benzene
Nuclear magnetic resonance
Networks (circuits)

All Science Journal Classification (ASJC) codes

  • Catalysis
  • Organic Chemistry

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Retro-Diels-Alder approach to the synthesis of π-expanded azuliporphyrins and their porphyrinoid aromaticity. / Okujima, Tetsuo; Kikkawa, Tasuku; Nakano, Haruyuki; Kubota, Hiroshi; Fukugami, Nobumasa; Ono, Noboru; Yamada, Hiroko; Uno, Hidemitsu.

In: Chemistry - A European Journal, Vol. 18, No. 40, 01.10.2012, p. 12854-12863.

Research output: Contribution to journalArticle

Okujima, Tetsuo ; Kikkawa, Tasuku ; Nakano, Haruyuki ; Kubota, Hiroshi ; Fukugami, Nobumasa ; Ono, Noboru ; Yamada, Hiroko ; Uno, Hidemitsu. / Retro-Diels-Alder approach to the synthesis of π-expanded azuliporphyrins and their porphyrinoid aromaticity. In: Chemistry - A European Journal. 2012 ; Vol. 18, No. 40. pp. 12854-12863.
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