Stereoselective Synthesis of Medium-sized Carbocyclic Compounds by Tandem Reactions of Cyclic Sulfur Ylides

环状硫叶立德串联反应立体选择性合成中型碳环化合物

• 批准号: 12650851
• 负责人: FUJIMOTO Tetsuya
• 金额: $ 2.37万
• 依托单位: SHINSHU UNIVERSITY
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 2000
• 资助国家: 日本
• 起止时间: 2000 至 2001
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-12650851/
• 关键词: Tandem reactions; Sulfur ylide; Medium-sized carbocycles; Stereoselective; Cyclopropane; Oxirane; Baylis - Hillman adduct

The reaction of a five-membered oxosulfonium ylide with acetates of Baylis - Hillman adducts afforded cycloheptene oxide derivatives with high stereoselectivity in 19-74 % yields via tandem Michael - intramolecular Corey -Chaykovsky reactions. The stereochemistry of resulting compounds was elucidated by an X-ray analysis. From the results of the stereochemistry, an intramolecular Corey reaction was implied to proceed via a rigid bicyclic intermediate containing a chair-form thiacyclohexane ring. In addition, the same reaction of the corresponding sixmembered sulfur ylide was investigated. Consequently, cyclooctene oxide derivatives were obtained in 7-46 % yields as a 4 : 1 mixture of diastereomers relevant to the configuration of sulfur atom. Moreover, the reactions of the cyclic sulfur ylides with aldehydes and enones were attempted in order to evaluate the reactivity of cyclic sulfur ylides. All of the reactions provided the Corey reaction products ( cyclopropane or oxirane derivatives ) in excellent yields. On the other hand, the reaction of the six-membered oxosulfonium ylide with 4-hexen-2-one in the presence of two equimolar amount of base gave a novel eight-membered carbocyclic compound ( 1 : 2 adduct of ylide and enone ) with high stereoselectivity.

五元氧锍叶立德与Baylis-Hillman加合物的乙酸酯的反应通过串联Michael-分子内Corey-Chaykovsky反应提供了具有高立体选择性的环庚烯氧化物衍生物，产率为19-74%。通过 X 射线分析阐明了所得化合物的立体化学。从立体化学的结果来看，分子内科里反应是通过含有椅形硫代环己烷环的刚性双环中间体进行的。此外，还研究了相应的六元硫叶立德的相同反应。因此，以与硫原子构型相关的非对映异构体的4:1混合物形式，以7-46%的收率获得环辛烯氧化物衍生物。此外，尝试了环状硫叶立德与醛和烯酮的反应以评价环状硫叶立德的反应性。所有反应均以优异的收率提供了科里反应产物（环丙烷或环氧乙烷衍生物）。另一方面，六元氧锍叶立德与4-己烯-2-酮在两等摩尔量的碱存在下反应，得到一种新型八元碳环化合物（叶立德和烯酮的1 : 2加合物），高立体选择性。

项目成果

Akiyama,Hitoshi: "Reactions of Cyclic Sulfur Ylides with Some Carbonyl Compounds"Heteroatom Chemistry. in press.

Akiyama，Hitoshi：“环状硫叶立德与一些羰基化合物的反应”杂原子化学。

Hitoshi Akiyama, Tetsuya Fujimoto, Iwao Yamamoto et al.: "Reactions of Cyclic Sulfur Ylides with Some Carbonyl Compounds"Heteroatom Chemistry. (印刷中).

Hitoshi Akiyama、Tetsuya Fujimoto、Iwao Yamamoto 等人：“环状硫叶立德与一些羰基化合物的反应”杂原子化学（正在出版）。

Hitoshi Akiyama, Tetsuya Fujimoto, Iwao Yamamoto et al.: "Stereoselective Synthesis of Medium-Sized Cyclic Compounds by the Tandem Reactions of a Cyclic Oxosulfonium Ylide with Acetates of the Baylis-"European Journal of Organic Chemistry. 2265-2272 (2001

Hitoshi Akiyama、Tetsuya Fujimoto、Iwao Yamamoto 等人：“通过环状氧代锍叶立德与贝里斯乙酸酯的串联反应合成中等大小环状化合物”-《欧洲有机化学杂志》。

Akiyama,Hitoshi: "Stereoselective Systhesis of Medium-Sized Cyclic Compounds by the Tandem Reactions of a Cyclic Oxosulfonium Ylide with Acetates of the Baylis - Hillman Adducts"European Journal of Organic Chemistry. 2265-2272 (2001)

Akiyama，Hitoshi：“通过环状氧代锍叶立德与贝里斯 - 希尔曼加合物乙酸酯的串联反应立体选择性合成中等大小的环状化合物”欧洲有机化学杂志。

Hitoshi Akiyama, Tetsuya Fujimoto, Iwao Yamamoto et al.: "Stereoselective Synthesis of Medium-Sized Cyclic Compounds by the Tandem Reactions of a Cyclic Oxosulfonium Ylide with Acetates of the Baylis-......."European Journal of Organic Chemistry. 2265-227

Hitoshi Akiyama、Tetsuya Fujimoto、Iwao Yamamoto 等人：“通过环状氧代锍叶立德与贝利斯乙酸酯的串联反应合成中等大小的环状化合物-......”欧洲有机化学杂志。