已经进行了醇钠醇盐与 (Me3Si)3CSi(C6H4-OMe-p)MeX 的反应。主要产品有:(Me3Si)2CHSi(An)Me(OR)和Me3SiCH2Si(An)Me(OR);An = (C6H4-OMe-p) and OR = OEt, OPr, O iso-Pr, OBu ,O 异丁基,O 异戊基,O 苄基,O 烯丙基,糠基。这表明该反应通过消除加成机制进行。我们感谢 M. Mahkam 博士的有益评论。
Quantitative substituent effects in the Grignard reaction with silanes
作者:Oleg Golubev、Dmitri Panov、Anu Ploom、Ants Tuulmets、Binh T. Nguyen
DOI:10.1016/j.jorganchem.2007.05.009
日期:2007.8
the resonance effect of substituents at least in nucleophilic displacement reactions at the silicon center. An attempt to calculate the steric constants for polarsubstituents was made. It appeared that the inductive constants σ∗ derived from the carbon chemistry are not applicable to the silicon chemistry. New scales of parameters for description of polar and steric effects in the organosilicon chemistry
The enantioselective construction of silicon-stereocenter by asymmetric enamine catalysis is reported. The reaction proceeds via an unprecedented desymmetric intramolecular aldolization of prochiral siladials for the diverse synthesis of multifunctional silicon-stereogenic silacycles.