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。tirs（rimehylsilyl）硅烷二羧酸盐与tris（三甲基甲硅烷基甲硅烷基）的Lequiv silyllihtium的反应给出了硫酸锂（三甲基甲硅烷基）硅酸盐（1）almos almos almos almos almos通过用甲基硅烷基甲硅烷基甲硅烷基组的lithom替换为Almos。 1与烷基卤化物和氯丙烷的进一步反应产生了高产量的Si-替代产物。相反，使用醛，它们给出了由添加反应引起的产品。他们与二氯化钯进行了氧化耦合，以产生二甲二羧酸盐。2。 Lihtium硅酸盐与酰基氯化物的反应产生了双乙酰胺。这是用两个或多个酰基基取代的Si原子的化合物的第一个合成。3。还研究了硅烯酸酯与乙酰烯酸酯的反应。锂硅酸盐与苯基取代的乙酰烯烯易于反应，使乙烯基苯甲酸酯具有良好的产率。相比之下，它们没有与烷基取代的乙炔反应。乙烯基烯基酯与氯硅烷反应，以良好的产率提供2-二利二烯衍生物。

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。