Comparisons of the reactivities of the tri-t-butyl- and tris(trimethylsilyl)methyl-silicon compounds
作者:Colin Eaborn、Anil K. Saxena
DOI:10.1016/0022-328x(84)85161-x
日期:1984.8
reactions of t-Bu3SiX (X usually I, but in some cases OSO2CF3 or Cl) and the corresponding TsiMe2X species (Tsi = Me3Si)3)C) have led to the following conclusions: (a) Under conditions in which TsiSiMe2I is thought to react via a silicocationic intermediate (mainly, solvolysis in CF3CO2H or reactions with silver salts), this iodide is much more reactive than t-Bu3SiI. (b) The reactivity difference between
比较t-Bu 3 SiX(X通常为I,但有时为OSO 2 CF 3或Cl)与相应的TsiMe 2 X物种(Tsi = Me 3 Si)3)C的反应,得出以下结论: :(a)在认为TsiSiMe 2 I通过硅阳离子中间体反应的条件下(主要是在CF 3 CO 2 H中的溶剂分解或与银盐的反应),该碘化物比t-Bu 3 SiI更具反应性。(b)两种碘化物之间的反应性差异在与碱金属盐的反应(即S N 2工艺,TsiSiMe 2)中显着减小我通常是。反应性提高了3–8倍。(c)在S N 2-中间机制可能起作用的条件下的甲醇水解和水解中,TsiSiMe 2 X和t-Bu 3 SiX化合物之间的反应性差异(X = I或OSO 2 CF 3)随介质的不同而有很大差异,前者通常(尽管并非总是如此)反应性更强,但差异远小于(a)中提到的反应中的区别,在该反应中,Si-X键容易断裂最大的主导因素。(d)在这些高