Intramolecular Anionic Diels-Alder Reactions of 1-Aryl-4-oxahepta-1,6-diyne Systems in DMSO
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- 作者：Takayuki Kudoh ; Tomoko Mori ; Mitsuhito Shirahama ; Masashi Yamada ; Teruhiko Ishikawa ; Seiki Saito ; Hisayoshi Kobayashi
- 刊名：Journal of the American Chemical Society
- 出版年：2007
- 出版时间：April 25, 2007
- 年：2007
- 卷：129
- 期：16
- 页码：4939 - 4947
- 全文大小：291K
- 年卷期：v.129,no.16(April 25, 2007)
- ISSN：1520-5126
文摘
Base-promoted cycloaddition reactions of 1-aryl- or 1-aryl-7-substituted-4-oxahepta-1,6-diynesystems in DMSO have proven to involve an anionic intramolecular Diels-Alder process taking place evenat room temperature in spite of the reaction suffering from temporary disruption of aromaticity. Althoughinitially formed 
-arylallenide anion can be protonated by DMSO, it can be back to the allenide anion probablybecause of a small acidity difference between -arylallene and DMSO. The -arylallenide anion incombination with the -aryl substituent can constitute an anionic diene structure that undergoes theintramolecular Diels-Alder reaction involving the C(6)-yne part, a very fast process probably because ofthe increased HOMO-1 level of the anionic diene, as shown by DFT calculations. Diversified substitutednaphthalenes, benzofurans, phenanthrenes, and quinolines, including biaryl architectures, are availablefrom 4-oxahepta-1,6-diynes in a highly expeditious way.
-arylallenide anion can be protonated by DMSO, it can be back to the allenide anion probablybecause of a small acidity difference between -arylallene and DMSO. The -arylallenide anion incombination with the -aryl substituent can constitute an anionic diene structure that undergoes theintramolecular Diels-Alder reaction involving the C(6)-yne part, a very fast process probably because ofthe increased HOMO-1 level of the anionic diene, as shown by DFT calculations. Diversified substitutednaphthalenes, benzofurans, phenanthrenes, and quinolines, including biaryl architectures, are availablefrom 4-oxahepta-1,6-diynes in a highly expeditious way.