Gau David, Kato Tsuyoshi, Saffon-Merceron Nathalie, Cossío Fernando P, Baceiredo Antoine
Universite de Toulouse, UPS, LHFA, and CNRS, LHFA UMR 5069, F-31062 Toulouse, France.
J Am Chem Soc. 2009 Jul 1;131(25):8762-3. doi: 10.1021/ja903540b.
The silicon congeners of well-known phosphonium ylides have been considered only as short-lived reactive intermediates. We successfully synthesized a remarkably stable phosphonium sila-ylide. Its X-ray structure reveals a long Si-P bond and a strongly pyramidalized silicon center, indicating a very weak P-Si pi interaction. In addition, it exhibits an alpha,beta-ambiphilic character with a nucleophilic silicon center, similar to its carbon-congener phosphonium ylides. This property of the phosphonium sila-ylide allows its use as a sila-Wittig reagent with carbonyl derivatives.
著名的鏻叶立德的硅类似物一直仅被视为寿命短暂的反应中间体。我们成功合成了一种稳定性极高的硅鏻叶立德。其X射线结构显示出一个长的Si-P键和一个高度锥形化的硅中心，这表明P-Si π相互作用非常弱。此外，它表现出α,β-双亲性，具有亲核性的硅中心，类似于其碳类似物鏻叶立德。硅鏻叶立德的这一性质使其能够用作与羰基衍生物反应的硅维蒂希试剂。
