4 3-Sulfoleneを利用する共役ジエン類の新しい立体選択的合成法 : その天然有機化合物合成への応用(口頭発表の部)

書誌事項

タイトル別名
  • 4 New stereoselective method for synthesizing conjugated dienes using 3-sulfolene as a masked diene synthon : Application to the syntheses of organic natural products
公開日
1987
DOI
  • 10.24496/tennenyuki.29.0_25
公開者
天然有機化合物討論会実行委員会

説明

Reaction of 3-sulfolenes with various electrophiles in combination with stereoselective desulfonylation provided a new method for synthesizing (E)-, (E,Z)-, and (E,E)-conjugated dienes with exceedingly high stereoselectivity. 3-Sulfolenes (1) react with primary alkyl iodides, aldehydes, ketones, and α,β-unsaturated ketones to give the corresponding α-substituted 3-sulfolenes. The substituents on the 3-sulfolene ring exhibit remarkable effect on the regioselectivity of the reaction with electrophiles. Electron donating groups on the double bond effect selective substitution at the 2-position, while electron withdrawing groups cause substitution at the 5-position. When one of the α-position of the sulfolene is occupied by an alkyl group, electrophiles are exclusively introduced to the other α-position. A new method is developed for desulfonylating trans-2,5-substituted 3-sulfolenes (4) exclusively to (E,E)-conjugated dienes (10). The method is applied to the highly stereoselective syntheses of three insect pheromones having conjugated diene structure and monoterpene (E)-tagetone (17). Convenient methods for synthesizing hydrindane derivatives are developed by utilizing the diene synthesis in combination with intramolecular Diels-Alder reaction. The method is applied to the completely stereoselective synthesis of coronafacic acid (22), and asymmetric synthesis of the CD-ring and C(20)-C(22) part of vitamin D (26).

収録刊行物

詳細情報 詳細情報について

  • CRID
    1390282681050057728
  • NII論文ID
    110006678616
  • DOI
    10.24496/tennenyuki.29.0_25
  • 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

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