Thiophene-fused bisdehydro[12]annulene that undergoes transannular alkyne cycloaddition by either light or heat

Aiko Fukazawa, Hiroya Oshima, Yoshihito Shiota, Shouya Takahashi, Kazunari Yoshizawa, Shigehiro Yamaguchi

Research output: Contribution to journalArticle

15 Citations (Scopus)

Abstract

A new bisdehydro[12]annulene derivative having a thiophene-fused structure has been synthesized. This highly twisted π-conjugated macrocycle with two acetylene moieties in close proximity produces a [2+2]-type alkyne cycloadduct by either photoirradiation or mild heating without any transition metals. Theoretical calculations reveal that the thermal reaction proceeds through successive 8π and 4π electrocyclic reactions, while the photochemical reaction is an asynchronous concerted [2+2] cycloaddition. The fused structure with the less-aromatic thiophene ring is crucial for achieving this reaction. The cycloadduct, thiophene-fused biphenylene, has significant potential as a new polycyclic π-scaffold for electronic applications.

Original languageEnglish
Pages (from-to)1731-1734
Number of pages4
JournalJournal of the American Chemical Society
Volume135
Issue number5
DOIs
Publication statusPublished - Feb 6 2013

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Thiophenes
Alkynes
Cycloaddition
Cycloaddition Reaction
Thiophene
Hot Temperature
Light
Acetylene
Photochemical reactions
Scaffolds
Heating
Transition metals
Metals
Derivatives

All Science Journal Classification (ASJC) codes

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

Cite this

Thiophene-fused bisdehydro[12]annulene that undergoes transannular alkyne cycloaddition by either light or heat. / Fukazawa, Aiko; Oshima, Hiroya; Shiota, Yoshihito; Takahashi, Shouya; Yoshizawa, Kazunari; Yamaguchi, Shigehiro.

In: Journal of the American Chemical Society, Vol. 135, No. 5, 06.02.2013, p. 1731-1734.

Research output: Contribution to journalArticle

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