58 環状アリルスルホニウムイリドのシグマトロピー転位とその天然物合成への応用(ポスター発表の部)

• 城戸 英郎

  東北大非水研

• 安彦 聡也

  東北大非水研

• カジ アブール・バシャール

  東北大非水研

• シンハ スバース・チャンドラ

  東北大非水研

• 加藤 紀元

  東北大非水研

• 吉越 昭

  東北大非水研

書誌事項

タイトル別名

• 58 Sigmatropic Rearrangement of Cyclic Allylsulfonium Ylides and Its Application to the Synthesis of Natural Products

抄録

The [2,3]sigmatropic rearrangement of cyclic allylsulfonium ylides(B), generated from the diazo malonate of Z-phenylthio-3-butenol derivatives(8a-8d) with catalytic amount of rhodium acetate in refluxing benzene, afforded γ,δ-unsaturated seven-membered lactones (9a-9d) in moderate yield. In a similar fashion, treatment of a diazo malonate,readily prepared from homologous alcohol(7e), with rhodium acetate provided eight-membered lactone(9e), albeit in low yield. On the other hand, this methodology was applied to the synthesis of six-membered spirolactones: treatment of α-diazo allylsulfides containing cyclopentene, cyclohexene or cycloheptene ring(16a-16c), which were prepared from corresponding cycloalkanone by a 9 step sequence, with rhodium acetate afforded the desired six-membered spirolactones(17a-17c) in excellent yields. An application of this rearrangement to the stereoselective synthesis of natural vernolepin(18) will also be discussed.

収録刊行物

• 天然有機化合物討論会講演要旨集

  天然有機化合物討論会講演要旨集 32 (0), 433-440, 1990

  天然有機化合物討論会実行委員会

詳細情報

• CRID: 1390001206074706688
• NII論文ID: 110006678931
• DOI: 10.24496/tennenyuki.32.0_433
• ISSN: 24331856
• 本文言語コード: ja
• データソース種別:
  • JaLC
  • CiNii Articles
• 抄録ライセンスフラグ: 使用不可