Forrmation of enolate-type anionic silicon species and their applications to the synthesis of novel organosilicon compounds

烯醇式阴离子硅的形成及其在新型有机硅化合物合成中的应用

• 批准号: 11650898
• 负责人: OHSHITA Joji
• 金额: $ 2.18万
• 依托单位: Hiroshima University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 1999
• 资助国家: 日本
• 起止时间: 1999 至 2000
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-11650898/
• 关键词: silicon; enolate; silene; silyllithium; シラジエン; アシルシラン; 有機ケイ素; カルボニル化合物; 有機リチウム

1. The reactions of tirs (rimehylsilyl) silanecarboxylates with lequiv of tris (trimethylsilyl) silyllihtium gave lithium alkoxybis (trimethylsilyl) silenolates (1) almos quantitatively by replacement of the trimethylsilyl group with a lithium atom. Further reaction of 1 with alkyl halides and chlorosilanes produced Si-substitution products in high yield. In contrast, with aldehydes, they gave products arising from addition reactions. They underwent oxidative coupling with palladium dichloride to give disilanedicarboxylates.2. The reactions of lihtium silenolates with acyl chlorides gave bis- and tetraacylsilanes. This is the first synthesis of compounds having an Si atom substituted with two or more acyl groups.3. The reactions of lithium silenolates with acetylenes were also studied. Lithium silenolates reacted readily with phenyl-substituted acetylenes to give ethenylsileolates in good yields. In contrast, they did not react with alkyl-substituted acetylenes. The ethenylsilenolates reacted with chlorosilanes to afford 2-siladiene derivatives in good yield.

1. 三（三甲基硅基）硅烷羧酸酯与三（三甲基硅基）硅基锂基的反应，通过用锂原子取代三甲基硅基，得到了几乎定量的烷氧双（三甲基硅基）硅烯酸锂(1)。1与卤代烃和氯硅烷进一步反应，得到高收率的硅取代产物。相反，对于醛，它们是由加成反应产生的产物。它们与二氯化钯氧化偶联得到二硅二羧酸盐。硅烯酸锂与酰基氯化物反应得到双酰基硅烷和四酰基硅烷。这是首次合成一个硅原子被两个或两个以上酰基取代的化合物。研究了硅醇酸锂与乙炔的反应。硅醇酸锂很容易与苯基取代乙炔反应，得到收率高的硅醇酸乙烯酯。相反，它们不与烷基取代乙炔反应。乙烯基硅烯酸酯与氯硅烷反应生成2-硅二烯衍生物，产率高。

项目成果

J.Ohshita: "Reactions of Lithium Silenolates with Acyl Halides, First Synthesis of Di-and Tetraacylsilanes"J.Am.Chem.Soc.. 121. 6088-6089 (1999)

J.Ohshita：“硅烯醇锂与酰基卤的反应，二酰基硅烷和四酰基硅烷的首次合成”J.Am.Chem.Soc.. 121. 6088-6089 (1999)

Joji Ohshita: "Reactions of Lithium Silenolates with Acyl halicles,First Synthesis of Di- and Tetraacyldsilanes"J.Am.Chem.Soc,. 121. 6080 (1999)

Joji Ohshita：“硅烯酸锂与酰基卤化物的反应，二酰基和四酰基硅烷的首次合成”J.Am.Chem.Soc，。

Joji Ohshita: "Formation and Reactions of Lithium Ester Silenolates : Silicon Analogs of Lithium Ester Enolates"Organometallics. 22. 4545-4551 (1999)

Joji Ohshita：“锂酯硅醇盐的形成和反应：锂酯烯醇化物的硅类似物”有机金属。

Joji Ohshita: "Reactions of Lithium Silenolates with Acetylenes, Formation and Characterization of 2-Siladienes"Organometallics. (in press).

Joji Ohshita：“硅烯酸锂与乙炔的反应，2-硅二烯的形成和表征”有机金属化合物。

J.Ohshita: "Formation and Reactions of Lithium Ester Silenolates : Silicon Analogs of Lithium Ester Enolates"Organometallics. 22. 4545-4551 (1999)

J.Ohshita：“锂酯硅醇盐的形成和反应：锂酯烯醇化物的硅类似物”有机金属。