3-(2-Diethoxyphosphoryl-2,2-difluoroethyl)-4-(iodomethyl)oxolane | 142635-56-1

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 有机膦酸及其衍生物
• 英文名称: 3-(2-Diethoxyphosphoryl-2,2-difluoroethyl)-4-(iodomethyl)oxolane
• CAS: 142635-56-1；142635-65-2
• 化学式: C₁₁H₂₀F₂IO₄P
• 分子量: 412.152
• InChiKey: FPBRPYPXRYYBBJ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.6
• 重原子数：
  19
• 可旋转键数：
  8
• 环数：
  1.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  44.8
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为产物：
  描述：

  烯丙基醚 、 diethyl iododifluoromethylphosphonate 在 四(三苯基膦)钯 作用下， 以82%的产率得到3-(2-Diethoxyphosphoryl-2,2-difluoroethyl)-4-(iodomethyl)oxolane
  参考文献：
  名称：

  A novel and practical preparation of .alpha.,.alpha.-difluoro functionalized phosphonates from iododifluoromethylphosphonate

  摘要：

  The addition reaction of iododifluoromethylphosphonate 1 with alkenes is catalyzed by tetrakis(triphenylphosphine)palladium or copper metal under mild conditions. A variety of functional groups, including alkyl, trimethylsilyl, hydroxy, epoxy, acetoxy, ketone, and ester, in the alkenes could be tolerated under the reaction conditions. Reaction of 2 equiv of 1 with dienes gives the corresponding bisphosphonates. Although the palladium complex fails to induce addition of 1 to cyclohexene, the addition reaction proceeds readily with copper at 85-degrees-C. With diallyl ether, a tetrahydrofuran derivative is obtained. Electron scavenger and radical inhibitors suppressed the addition reaction completely. A single electron transfer initiated radical mechanism is proposed. Treatment of the adducts with zinc in the presence of nickel chloride in moist THF at room temperature provides the corresponding alpha,alpha-difluoro-functionalized phosphonates in good yields.

  DOI：

  10.1021/jo00043a027

文献信息

• A novel and practical preparation of .alpha.,.alpha.-difluoro functionalized phosphonates from iododifluoromethylphosphonate
  作者：Zhen Yu Yang、Donald J. Burton

  DOI：10.1021/jo00043a027

  日期：1992.8

  The addition reaction of iododifluoromethylphosphonate 1 with alkenes is catalyzed by tetrakis(triphenylphosphine)palladium or copper metal under mild conditions. A variety of functional groups, including alkyl, trimethylsilyl, hydroxy, epoxy, acetoxy, ketone, and ester, in the alkenes could be tolerated under the reaction conditions. Reaction of 2 equiv of 1 with dienes gives the corresponding bisphosphonates. Although the palladium complex fails to induce addition of 1 to cyclohexene, the addition reaction proceeds readily with copper at 85-degrees-C. With diallyl ether, a tetrahydrofuran derivative is obtained. Electron scavenger and radical inhibitors suppressed the addition reaction completely. A single electron transfer initiated radical mechanism is proposed. Treatment of the adducts with zinc in the presence of nickel chloride in moist THF at room temperature provides the corresponding alpha,alpha-difluoro-functionalized phosphonates in good yields.