Novel preparation method and synthetic applications of cyclopropyl trimethylsilyl ketones

环丙基三甲基硅酮的制备新方法及合成应用

• 批准号: 62550627
• 负责人: NAKAJIMA Tadashi
• 金额: $ 1.15万
• 依托单位: Kanazawa University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for General Scientific Research (C)
• 财政年份: 1987
• 资助国家: 日本
• 起止时间: 1987 至 1988
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-62550627/
• 关键词: Cyclopropyl silyl ketones; 1-Silyl-1-cyclopropylalkenes; Siloxyalkenes; -Ketosilanes; Alkylidenephosphoranes; オキソスルホニウムメチリド; 2-シリルジヒドロフラン; シクロブタノン; 硫黄イリド; β-ケトシラン; 1-シリルー1-シクロプロピルアルケン; リンイリド

A series of new cyclopropyl trimethylsilyl ketones has been prepared in moderate yield from the novel reaction of 1-trimethylsilylcyclopropyllithium derivartives with dichloromethyl methyl ether. This reaction involves the intramolecular 1,2-silicon shift from carbon to carbon. The spectroscopic properties of these silyl ketones have been measured.The ketones obtained here react with various halogen acids under milder conditions compared to that of their carbon analogs to give the ring opening products, 3-chloropropyl silyl ketones, or the ring enlargement products, 2-silyl-4,5-dihydrofuran derivatives in some cases. The reaction with sulfuric acid or trifluoromethane sulfonic acid affords only the corrensponding silyldihydrofurans in good yield. Especially, it is noteworty that the reaction of 2-phenylcyclopropyl silyl ketone with sulfuric acid yields 2-phenylcyclobutanone. The formation of these comounds is interpreted on the basis of the effect that silicon stabilizes a cation to it … More .Wittig reactions of cyclopropyl silyl ketones with alkylidene-triphenylphosphoranes proceed stereoselectively to give the corresponding Z-1-silyl-1-cyclopropyl alkenes. The protiodesilylation of silyl cyclopropyl alkenes with tetrabutylammonium fluoride proceeds with retention of configuration to give E-cyclopropyl alkenes, although the reaction with hydrogen halides was unsuccessful due to the cleavage of the three membered ring.The reaction of sulfur ylides in THF with cyclopropyl silyl ketones resulted in the formation of the corresponding siloxyalkenes or -ketosilanes. The relative ratio of these compounds varies with the reaction temperature, the porality of solvents used, and the preparation method of ylide. It is noteworthy that the reaction with salt free ylide affords siloxyalkenes and that of the ylide containing inorganic salt -ketosilanes, selectively. These two type of products would be formed by the anionotropic and cationotropic rearrangement of silyl group in the betaine intermediate. Less

通过1-三甲基硅基环丙基锂衍生物与二氯甲基甲基醚的新反应，以中等产率制备了一系列新的环丙基三甲基硅基酮。该反应涉及分子内 1,2-硅从碳到碳的转变。已经测量了这些甲硅烷基酮的光谱性质。与碳类似物相比，这里获得的酮在更温和的条件下与各种卤酸反应，得到开环产物3-氯丙基甲硅烷基酮，或在某些情况下得到扩环产物2-甲硅烷基-4,5-二氢呋喃衍生物。与硫酸或三氟甲磺酸的反应仅以良好的产率提供相应的甲硅烷基二氢呋喃。尤其值得注意的是，2-苯基环丙基甲硅烷基酮与硫酸反应生成2-苯基环丁酮。这些化合物的形成是基于硅稳定其阳离子的作用来解释的。环丙基甲硅烷基酮与亚烷基-三苯基正膦的维蒂希反应立体选择性地进行，得到相应的 Z-1-甲硅烷基-1-环丙基烯烃。甲硅烷基环丙基烯烃与四丁基氟化铵进行脱甲硅烷基化，并保留构型，得到正环丙基烯烃，尽管由于三元环断裂，与卤化氢的反应不成功。硫叶立德在THF中与环丙基甲硅烷基酮反应，导致形成相应的 硅氧基烯烃或-酮硅烷。这些化合物的相对比例随反应温度、所用溶剂的极性以及叶立德的制备方法而变化。值得注意的是，与无盐叶立德的反应选择性地提供甲硅烷氧基烯烃和含有无机盐叶立德的酮硅烷。这两类产物是由甜菜碱中间体中甲硅烷基的阴离子型和阳离子型重排形成的。较少的

项目成果

Tadashi,NAKAJIMA: Chemistry letters. 181-182 (1986)

中岛正：化学信件。

Tadashi NAKAJIMA; Hiroyuki MIYAJI; Masahito SEGI; Sohei SUGA: "Ring opening and enlargement of cyclopropyl trimethylsilyl ketones by acids." Chemistry Letters. 181-182 (1986)

中岛正；

Tadashi NAKAJIMA: Bull. Chem. Soc. Jpn.

中岛正：公牛。

Tadashi NAKAJIMA: Chemistry Letters. 177-180 (1986)

中岛正：化学快报。

Tadashi NAKAJIMA: Chemistry letters. 181-182 (1986)

中岛正：化学信件。