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 journalArticlepeer-review

20 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

All Science Journal Classification (ASJC) codes

  • Catalysis
  • Organic Chemistry

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