New Development of Organic Syntheses mediated by Functional Allene Intermediates

功能性丙二烯中间体介导的有机合成新进展

• 批准号: 18590021
• 负责人: SHIOIRI Takayuki
• 金额: $ 2.57万
• 依托单位: Meijo University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 2006
• 资助国家: 日本
• 起止时间: 2006 至 2007
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-18590021/
• 关键词: β-substituted Morita-Baylis-Hillman type compound; (Z)-chalcone; siloxyallene intermediates; potassium tert-butoxide; カリウムtert-ブトキシド; β-置換Morita-Baylis-Hillmanタイプ化合物; (Ζ)-カルコン; (Ζ)-選択的反応

We have already developed a new tandem addition-isomerization-sily1 aldol reaction of aromatic aldehydes with phenyltrimethylsilylacetylene catalyzed by a quaternary ammonium fluoride derived from cinchonine, giving (Z)-β-substituted Morita-Baylis-Hillman type compounds via siloxyallenes as functional allenes. As an extension of this reaction, treatment of O-trimethylsily1 derivatives of propargyl alcohols having the aromatic functions at the both terminals with potassium tertbutoxide was found to produce siloxyallene intermediates, which react with various aldehydes to furnish (Z)-β-substituted Morita-Baylis-Hillman type compounds. This reaction will be called a tandem isomerization-silylaldol reaction. In place of aldehydes, treatment of siloxyallene intermediates with sulfuric acid stereoselectively affords (Z)-chalcones. The siloxyallene intermediates will be expected to produce a variety of (Z)-β-substituted Morita-Baylis-Hillman type compounds by the reaction with the other electrophiles.

我们已经开发了一种新的芳香醛与苯基三甲基硅基乙炔的串联加成-异构化-硅羟基乙醛反应，得到了(Z)-β取代的以硅氧基烯为功能烯的Morita-Baylis-Hillman型化合物。作为该反应的延伸，用叔丁醇钾处理具有两端芳香功能的丙叉醇的O-三甲基硅基衍生物生成硅氧烯中间体，这些中间体与各种醛反应得到(Z)-β取代的Morita-Baylis-Hillman型化合物。这个反应将被称为串联异构化-硅醛反应。取代醛，用硫酸处理硅氧烯中间体，立体选择性地得到(Z)-查尔酮。硅氧烯中间体有望与其他亲电体反应生成多种(Z)-β取代的Morita-Baylis-Hillman型化合物。

项目成果

Convenient stereoselective synthesis of (Z)-chalcone derivatives from 1,3-diaryl-2-propynyl silyl ethers

• DOI: 10.1016/j.tetlet.2006.05.021
• 发表时间: 2006-07
• 期刊: Tetrahedron Letters
• 影响因子: 1.8
• 作者: K. Yoshizawa;T. Shioiri*

Siloxyallenes revisited. A useful functional intermediate for the Synthesis of β-branched Morita-Baylis-Hillman-type adducts and (Z)-chalcones

重新审视硅氧基联烯。用于合成 β-支链 Morita-Baylis-Hillman 型加合物和 (Z)-查尔酮的有用功能中间体。

• 发表时间: 2007
• 期刊: Tetrahedron 63
• 作者: Kazuhiro Yoshizawa;Takayuki Shioiri
• 通讯作者: Takayuki Shioiri

Synthesis of β-branched Morita–Baylis–Hillman-type adducts from 1,3-diaryl-2-propynyl trimethylsilyl ethers and aldehydes catalyzed by potassium tert-butoxide

• DOI: 10.1016/j.tetlet.2005.11.118
• 发表时间: 2006-01
• 期刊: Tetrahedron Letters
• 影响因子: 1.8
• 作者: K. Yoshizawa;T. Shioiri*

Siloxyallenes revisited. A useful functional intermediate for the Synthesis of β-branched Morita-Baylis-Hillman-type adducts and (Ζ)-chalcones

重新审视硅氧基联烯。用于合成 β-支链 Morita-Baylis-Hillman 型加合物和 (Ζ)-查耳酮的有用功能中间体。

• 发表时间: 2007
• 期刊: Tetrahedron 63
• 作者: Kazuhiro Yoshizawa;Takayuki Shioiri
• 通讯作者: Takayuki Shioiri

Siloxyallenes revisited.A useful functional intermediate for the Synthesis of β-branched Morita-Baylis-Hillman-type adducts and (Z)-chalcones

重新审视硅氧基联烯。一种有用的中间体功能中间体，用于合成 β-支链 Morita-Baylis-Hillman 型加合物和 (Z)-查耳酮

• 发表时间: 2007
• 期刊: Tetrahedron 63
• 作者: Kazuhiro Yoshizawa;Takayuki Shioiri
• 通讯作者: Takayuki Shioiri