| 135721-33-4

• CAS: 135721-33-4
• 化学式: C₂₅H₁₄O₁₁P₂W₂
• 分子量: 920.027
• InChiKey: BDHQTBVCSDQYMZ-UHFFFAOYSA-N

反应信息

• 作为产物：
  描述：

  三甲基氯硅烷 、 在 盐酸 作用下， 以 四氢呋喃 为溶剂， 以25%的产率得到
  参考文献：
  名称：

  Reaction of 1,3-diphospholyl anions with chlorotrimethylsilane: [1,5]-sigmatropic shifts of the trimethylsilyl group around the 1,3-diphospholyl ring

  摘要：

  The protonation of the 4,5-diphenyl-1,3-diphosphoyl anion, [(PhC)2P2CH]-, in the presence of N-phenylmaleimide affords the [4 + 2] cycloadduct of the transient 4,5-diphenyl-2H-1,3-diphosphole, [(PhC)2P2CH2]. The silylation by chlorotrimethylsilane of the [P.W(CO)5]2 complex of this same anion at room temperature affords the corresponding complex of 1-(trimethylsilyl)-4,5-diphenyl-1H-1,3-diphosphole as the sole observable product. However, this 1,3-diphosphole complex is in equilibrium at room temperature 2-(trimethylsilyl)-4,5-diphenyl-2H-1,3-diphosphole via [1,5]-sigmatropic shifts of the silyl group. This 2H-1,3-diphosphole complex can be trapped as a [4 + 2] cycloadduct with dimethyl acetylenedicarboxylate. At -80-degrees-C, these [1,5] shifts are frozen out and the silylation of the same complexed anion takes place exclusively at the carbons of the ring to give the 2-(trimethylsilyl)-4,5-diphenyl-2H-1,3-diphosphole and the 4-(trimethylsilyl)-4,5-diphenyl-4H-1,3-diphosphole complexes whose formation is demonstrated by trapping with dimethyl acetylenedicarboxylate.

  DOI：

  10.1021/om00054a056