Intramolecular anionic Diels-Alder reactions of 1-aryl-4-oxahepta-1,6-diyne systems in DMSO

Takayuki Kudoh, Tomoko Mori, Mitsuhito Shirahama, Masashi Yamada, Teruhiko Ishikawa, Seiki Saito, Hisayoshi Kobayashi

Research output: Contribution to journalArticle

43 Citations (Scopus)

Abstract

Base-promoted cycloaddition reactions of 1-aryl- or 1-aryl-7-substituted-4- oxahepta-1,6-diyne systems in DMSO have proven to involve an anionic intramolecular Diels-Alder process taking place even at room temperature in spite of the reaction suffering from temporary disruption of aromaticity. Although initially formed α-arylallenide anion can be protonated by DMSO, it can be back to the allenide anion probably because of a small acidity difference between α-arylallene and DMSO. The α-arylallenide anion in combination with the α-aryl substituent can constitute an anionic diene structure that undergoes the intramolecular Diels-Alder reaction involving the C(6)-yne part, a very fast process probably because of the increased HOMO-1 level of the anionic diene, as shown by DFT calculations. Diversified substituted naphthalenes, benzofurans, phenanthrenes, and quinolines, including biaryl architectures, are available from 4-oxahepta-1,6-diynes in a highly expeditious way.

Original languageEnglish
Pages (from-to)4939-4947
Number of pages9
JournalJournal of the American Chemical Society
Volume129
Issue number16
DOIs
Publication statusPublished - Apr 25 2007

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Cycloaddition Reaction
Dimethyl Sulfoxide
Anions
Negative ions
Phenanthrenes
Diynes
Benzofurans
Naphthalenes
Quinolines
Cycloaddition
Naphthalene
Acidity
Discrete Fourier transforms
Temperature

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

Intramolecular anionic Diels-Alder reactions of 1-aryl-4-oxahepta-1,6-diyne systems in DMSO. / Kudoh, Takayuki; Mori, Tomoko; Shirahama, Mitsuhito; Yamada, Masashi; Ishikawa, Teruhiko; Saito, Seiki; Kobayashi, Hisayoshi.

In: Journal of the American Chemical Society, Vol. 129, No. 16, 25.04.2007, p. 4939-4947.

Research output: Contribution to journalArticle

Kudoh, Takayuki ; Mori, Tomoko ; Shirahama, Mitsuhito ; Yamada, Masashi ; Ishikawa, Teruhiko ; Saito, Seiki ; Kobayashi, Hisayoshi. / Intramolecular anionic Diels-Alder reactions of 1-aryl-4-oxahepta-1,6-diyne systems in DMSO. In: Journal of the American Chemical Society. 2007 ; Vol. 129, No. 16. pp. 4939-4947.
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