Studies on Synthetic Utilities, Properties, and Functionalities of Novel Acylsilanes

新型酰基硅烷的合成用途、性质和功能研究

• 批准号: 13650922
• 负责人: OHSHITA Joji
• 金额: $ 2.24万
• 依托单位: KYUSHU UNIVERSITY
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 2001
• 资助国家: 日本
• 起止时间: 2001 至 2002
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-13650922/
• 关键词: Acylsilane; Silene; Cope rearrangement; Thermal isomerization; Enolate anion; 有機ケイ素化合物; 有機リチウム; Cope転位

To know the synthetic utilities of acylpolysilanes, three novel types of acylpolysilanes were prepared and their thermal isomerization was studied and found that they may be useful precursors for linear conjugated silenes, as summarized bellow. In addition, it was found that the reactions of silaenolates prepared from acylpolysilanes with benzophenone readily produced dioxasilacyclopentane derivatives in good yields. These results clearly indicate that the acylpolysilanes are useful for the preparation of novel silicon reactive species as well as that of cyclic organosilicon compounds.1) It was found that the reactions of lithium silaenolates with phenyl-substituted acetylenes afforded acyl-(Z)-ethenyldisilane as the first example of α-functionalized acylpolysilanes. Acylethenyldisilanes thus obtained underwent unique isomerization at >100 degree C via 2-siladiene intermediates. This appears to be an important methodology to produce siladiene at rather low temperature.2) Thermal isomerization of a bis(acyl)disilane involving a 2,3-disiladiene intermediate, leading to the formation of a 1,2-disilacyclobuene derivative was investigated3) Thermal isomerization of compounds having two acyl groups linked by a cycloalkane bridge took place at >120 degree C to give the respective ring-enlarged products. This is the first observation of oxa-Cope rearrangement of silenes.

为了了解酰基聚硅烷的合成用途，制备了三种新型的酰基聚硅烷，并对它们的热异构化进行了研究，发现它们可能是线性共轭硅烷的有用前体，如下所述。此外，还发现以酰基聚硅烷为原料制备的硅烯醇酯与二苯甲酮反应容易生成二氧硅环戊烷衍生物，收率较高。这些结果清楚地表明，酰基聚硅烷可用于制备新型硅活性物质和环有机硅化合物。1)硅烯醇酸锂与苯基取代乙炔的反应产生了α-功能化酰基聚硅烷的第一个例子-酰基-(Z)-乙烯基二硅烷。由此得到的酰基二硅烷在bbb100℃下通过2-硅二烯中间体进行了独特的异构化。这似乎是在相当低的温度下生产硅二烯的重要方法。2)研究了含有2,3-二二烯中间体的双（酰基）二硅烷的热异构化反应，生成1,2-二二烯衍生物。3)由环烷烃桥连接的两个酰基的化合物在bb0 - 120℃的温度下进行了热异构化反应，得到了各自的扩环产物。这是首次观察到oxa-Cope对沉默的重排。

项目成果

Joji Ohshita: "Oxa-Cope Rearrangement of Silenes Thermally Generated from 1,2-Bis[tris(trimethylsilyl)silylcarbonyl]alkanes"Journal of the American Chemical Society. 123. 8400-9401 (2001)

Joji Ohshita：“1,2-双[三（三甲基甲硅烷基）甲硅烷基羰基]烷烃热生成的硅烯的 Oxa-Cope 重排”美国化学会杂志。

Joji Ohshima: "Thermal Isomerization of 1,2-Diadamantoyltetrakis(trimethylsilyl)disilane via a 2,3-Disilabutadiene Intermediate"Journal of Organometallic Chemistry. (in press).

Joji Ohshima：“通过 2,3-二硅杂丁二烯中间体进行 1,2-二金刚烷酰基四（三甲基甲硅烷基）乙硅烷的热异构化”有机金属化学杂志。

Joji Ohshita: "Thermal Isomerization of an Acyl(ethenyl)disilane via 2-Siladiene Intermediates"Journal of Organometallic Chemistry. (印刷中).

Joji Ohshita：“通过 2-Siladiene 中间体进行酰基（乙烯基）乙硅烷的热异构化”有机金属化学杂志（正在出版）。

Joji Ohshita: "Reactions of Lithium Silenolates with Acetylenes, Formation and Characterization of 2-Siladienes"Organometallics. 20・6. 1065-1070 (2001)

Joji Ohshita：“硅烯醇锂与乙炔的反应，2-硅二烯的形成和表征”有机金属学 1065-1070。

Joji Ohshima: "Thermal Isomerization of an Acyl(ethenyl)disilane via 2-Siladiene Intermediates"Organometallics. (in press).

Joji Ohshima：“通过 2-Siladiene 中间体进行酰基（乙烯基）乙硅烷的热异构化”有机金属化合物。