Cyclohexen-1-yl-diphenyl-sulfanylidene-lambda5-phosphane | 66295-78-1

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: Cyclohexen-1-yl-diphenyl-sulfanylidene-lambda5-phosphane
• 英文别名: cyclohexen-1-yl-diphenyl-sulfanylidene-λ5-phosphane
• CAS: 66295-78-1
• 化学式: C₁₈H₁₉PS
• 分子量: 298.389
• InChiKey: UXVHPDSOHSRQAS-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.9
• 重原子数：
  20
• 可旋转键数：
  3
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.22
• 拓扑面积：
  32.1
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  Cyclohexen-1-yl-diphenyl-sulfanylidene-lambda5-phosphane 在 lithium aluminium tetrahydride 作用下， 以 四氢呋喃 为溶剂， 以59%的产率得到cyclohexyldiphenylphosphine sulfide
  参考文献：
  名称：

  钯催化酮类合成乙烯基膦

  摘要：

  据报道，钯催化的三氟甲基丙烯酸酯转化为乙烯基膦。该方法允许从酮合成乙烯基膦。据报道，对各种酮进行选择性烯醇化，然后随着三氟甲磺​​酸乙烯酯的捕获而捕获烯醇化物。然后通过钯催化将乙烯基三氟甲磺酸酯转化为相应的乙烯基膦。然后可以将所得的乙烯基膦还原为烷基膦。

  DOI：

  10.1016/s0040-4039(99)01819-5
• 作为产物：
  描述：

  在 1,2,3,4,5,6,7,8-八硫杂环辛烷 、 (S)-(+)-di-μ-chloro-bis[1-[(dimethylamino)ethyl]-2-naphthyl-C,N]dipalladium(II) 、 potassium carbonate 作用下， 以 四氢呋喃 为溶剂， 反应 14.33h， 生成 Cyclohexen-1-yl-diphenyl-sulfanylidene-lambda5-phosphane
  参考文献：
  名称：

  钯环催化烯基锍盐与二芳基膦的烯烃 C-P 交叉偶联得到烯基膦

  摘要：

  报道了烯基锍盐与仲二芳基膦的有效烯烃 C-P 交叉偶联。使用钯环可以在温和条件下耐受多种官能团的烯基锍盐的烯基部分轻松形成 C-P 键。该协议提供了一种以良好至高产率和高水平立体选择性 ( E选择性) 的方式轻松获取各种烯基膦产品的途径。

  DOI：

  10.1021/acs.organomet.2c00330

文献信息

• β Effect of Phosphorus Functionalities
  作者：Joseph B. Lambert、Yan Zhao

  DOI：10.1021/ja9537181

  日期：1996.1.1

  Diphelnylphosphinoyl (-P(=O)Ph(2)) and diphenylthiophosphinoyl (-P(=S)Ph(2)) respectively are modest and strong p-effect functionalities. When these groups are antiperiplanar to mesylate, the substrates solvolyze through unimolecular ionization. In contrast, substrates with the synclinal (gauche) arrangement react bimolecularly with solvent. The anti/gauche rate ratio is 440 for the oxide and 3.2 x 10(6) for the sulfide at 25 degrees C. The antiperiplanar sulfide in fact reacts 220 times more rapidly than the analogous cyclohexyl substrate at 25 degrees C, despite the strong electron-withdrawing nature of diphenylthiophosphinoyl. The a-secondary hydrogen/deuterium kinetic isotope effects of 1.21 for the anti oxide and 1.26 for the anti sulfide suggest kigh sp(2) character in the transition state, as expected for stabilization by hyperconjugation in a vertical mechanism. Energies calculated at the MP2 level show that the geometry with the P-C bond parallel to the empty carbocation p orbital is more stable than the perpendicular geometry by 22.94 kcal mol(-1) for PH2, 8.80 kcal mol(-1) for P(O)H-2, and 10.54 kcal mol(-1) for P(S)H-2, confirming significant hyperconjugation for these substituents. The global minimum, however, is the bridged structure (four-membered rings for the oxide and sulfide, three-membered ring for the simple phosphine), so that the mechanistic choice between a vertical mechanism (hyperconjugation) and a nonvertical mechanism (bridging) is not clear-cut.