A convenient synthetic method for preparing 2,5-disubstituted 1,6- methano[10]annulenes from 1,6-diacetylcyclohepta-1,3,5-triene

Shigeyasu Kuroda*, Shengli Zuo, Mitsunori Oda, Atsushi Fukuta, Takanori Kajioka, Toyohiko Saito, Shinji Furuta, Hitoshi Tsukumo, Kenji Sano, Ryuta Miyatake, Shozo Tomoda, Chiharu Hayakawa, Haruna Nozawa

*この論文の責任著者

研究成果: ジャーナルへの寄稿学術論文査読

8 被引用数 (Scopus)

抄録

The reaction of 1,6-diacetylcyclohepta-1,3,5-triene with various Grignard reagents gave high yields of addition products 5, which were treated with a catalytic amount of p-toluenesulfonic acid or pyridinium p- toluenesulfonate to afford 2,5-disubstituted 2,3-dihydro-1,6- methano[10]annulenes 6 via 1,6-bis(1-substituted vinyl)cyclohepta-1,3,5- trienes 8 and 2,5-disubstituted 3,4-dihydro-1,6-methano[10]annulenes 9. On the other hand, reactions under more forcing conditions gave the rearrangement products: 4,7-disubstituted 1,2-benzocyclohepta-1,3-dienes 7. The oxidation of 6 with 2,3-dichloro-5,6-dicyano-1,4-benzoquinone gave the 2,5-disubstituted 1,6-methano[10]annulens 4 in moderate-to-good yields. Conversion from 5 into 4 can be achieved by a one-flask procedure, providing a convenient synthetic method for preparing the title annulenes, particularly 2,5-diaryl ones. The reaction mechanism from 8 to 6, 7, and 9 is discussed on the basis of semiempirical molecular orbital calculations.

本文言語英語
ページ(範囲)1659-1671
ページ数13
ジャーナルBulletin of the Chemical Society of Japan
73
7
DOI
出版ステータス出版済み - 2000/07

ASJC Scopus 主題領域

  • 化学一般

フィンガープリント

「A convenient synthetic method for preparing 2,5-disubstituted 1,6- methano[10]annulenes from 1,6-diacetylcyclohepta-1,3,5-triene」の研究トピックを掘り下げます。これらがまとまってユニークなフィンガープリントを構成します。

引用スタイル