New Development of Organic Syntheses mediated by Functional Allene Intermediates

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。

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.