Budget Amount *help |
¥3,600,000 (Direct Cost: ¥3,600,000)
Fiscal Year 2006: ¥1,400,000 (Direct Cost: ¥1,400,000)
Fiscal Year 2005: ¥2,200,000 (Direct Cost: ¥2,200,000)
|
Research Abstract |
(1) Functional group transformations of 7-silanorbornadiene derivatives have been investigated. The 7-mesityl-7-silanorbornadiene was prepared and converted into the 7-chloro derivative. Reductive lithiation of the 7-chloro derivative with lithium naphthalenide afforded the silyllithium, which reacted with Me_3SiCl and MeI. The reactions of the 7-chloro derivative with n-BuLi and PhNHLi gave the 7-butyl derivative and the 7-amino derivative, respectively. Each stereochemistry during these transformations was determined by X-ray crystallographic analysis. (2) To investigate the intramolecular 1,5-type C^-.-Si interaction, [2-(trimethylsilyl)phenyl] phosphonium methylides were prepared. Treatment of their precursors, the methyl [2-(trimethylsilyl)phenyl] phosphonium iodides, with sodium hexamethyldisilazide in THE afforded the phosphonium methylides, which readily underwent anionic 1,4-silyl migration to form the silylated ylides at low temperatures. They were characterized by NMR and trapping experiments. (3) ο-[(Dimesitylboryl)phenyl] dimethylsilane underwent dehydrogenative condensation with alcohols and amines, giving the corresponding alkoxysilanes and aminosilanes in moderate to high yields. It is plausible that the ortho-boryl group electrophilically activates the Si-H bond.
|