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

1.三（三甲基硅基）硅羧酸锂与一当量三（三甲基硅基）硅锂反应，通过锂原子取代三甲基硅基，定量地得到烷氧基双（三甲基硅基）硅烯醇锂（1）。1与烷基卤化物和氯硅烷的进一步反应以高产率产生Si取代产物。与此相反，与醛，他们得到的产品所产生的加成反应。它们与二氯化钯进行氧化偶联得到二硅烷二羧酸酯.硅烯醇锂与酰氯反应生成双、四酰基硅烷。这是首次合成具有被两个或更多个酰基取代的Si原子的化合物。研究了硅烯醇锂与乙炔的反应。硅烯醇锂与苯基取代的炔类反应容易得到乙烯基硅烯醇锂，产率高。相反，它们不与烷基取代的乙炔反应。乙烯基硅烯醇化物与氯硅烷反应，以良好的产率得到2-硅杂二烯衍生物。

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.