安定に単離できる５員環アルキン化合物

• 鈴木 教之

  理化学研究所化学分析チーム」

書誌事項

タイトル別名

• Stable Five-Membered Cyclic Alkynes
• アンテイ ニ タンリデキル 5インカン アルキン カゴウブツ

抄録

It is generally known that small cyclic alkynes such as cyclopentyne is extremely reactive and unstable. Therefore it has been believed impossible to isolate cyclopentyne compounds.<BR>We recently reported that low-valent group 4 metallocenes reacted with 1, 2, 3-butatrienes to give 1-metallacyclopent-3-yne complexes and that resulted compounds are surprisingly stable and isolable. We succeeded in determination of their molecular structures by X-ray diffraction analyses, and showed that these are five-membered cyclic alkynes, while π, π-interaction of butatriene was also suggested. In this review, the preparation, structure and reactivity of these 1-metallacyclopent-3-yne compounds are described.<BR>The 1-zirconacyclopent-3-yne complexes reacted with another 'zirconocene' to form bimetallic complexes in which the cyclic alkyne coordinated to the other zirconocene moiety, indicating that the zirconacyclopentyne behaved as an alkyne. Seven-membered cyclic alkynes were also prepared from 1, 2, 3-butatriene and a zirconocene-alkyne compound. Protonolysis and subsequent nucleophilic attack to aldehyde gave allenyl or dienyl alcohol depending on proton source.

収録刊行物

• 有機合成化学協会誌

  有機合成化学協会誌 65 (4), 347-357, 2007

  公益社団法人 有機合成化学協会

キーワード

• cyclopentyne
• cyclic alkyne
• zirconium
• titanium
• hafnium
• butatriene

詳細情報

• CRID: 1390282680289342464
• NII論文ID: 10018898823
• NII書誌ID: AN0024521X
• DOI: 10.5059/yukigoseikyokaishi.65.347
• COI: 1:CAS:528:DC%2BD2sXktlCiur8%3D
• ISSN: 18836526
• ISSN: 00379980
• NDL書誌ID: 8788689
• Web Site: https://ndlsearch.ndl.go.jp/books/R000000004-I8788689
• 本文言語コード: ja
• データソース種別:
  • JaLC
  • NDL
  • Crossref
  • CiNii Articles
  • KAKEN
• 抄録ライセンスフラグ: 使用不可