1-Cyclohexyl-1-(diphenyl-phosphinoyl)-pentan-2-one | 172513-30-3

• 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: 1-Cyclohexyl-1-(diphenyl-phosphinoyl)-pentan-2-one
• 英文别名: 1-cyclohexyl-1-diphenylphosphorylpentan-2-one
• CAS: 172513-30-3
• 化学式: C₂₃H₂₉O₂P
• 分子量: 368.456
• InChiKey: GMRJSDKABZDGCK-UHFFFAOYSA-N

物化性质

• 沸点：
  485.4±28.0 °C(Predicted)
• 密度：
  1.10±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  5.32
• 重原子数：
  26.0
• 可旋转键数：
  7.0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.43
• 拓扑面积：
  34.14
• 氢给体数：
  0.0
• 氢受体数：
  2.0

反应信息

• 作为反应物：
  描述：

  1-Cyclohexyl-1-(diphenyl-phosphinoyl)-pentan-2-one 在 sodium tetrahydroborate 、 cerium(III) chloride 作用下， 以 乙醇 为溶剂， 以84%的产率得到(R*,S*)-1-Cyclohexyl-1-diphenylphosphinoylpentan-2-ol
  参考文献：
  名称：

  氧化膦的立体选择性霍纳-维蒂希反应：通过卢氏还原反应合成受阻的z烯烃

  摘要：

  当在新的CC双键旁边有支链时，与氧化膦反应的Horner-Wittig反应的自然抗选择性降低。更好的方法是将相应的酮Luche还原成相应的酮，当将支链置于C上时具有较高的抗选择性。氧化膦旁的侧链。

  DOI：

  10.1016/0040-4039(95)01629-v
• 作为产物：
  描述：

  1-Cyclohexyl-1-diphenylphosphinoylpentan-2-ol 在 重铬酸吡啶 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 以96%的产率得到1-Cyclohexyl-1-(diphenyl-phosphinoyl)-pentan-2-one
  参考文献：
  名称：

  氧化膦的立体选择性霍纳-维蒂希反应：通过卢氏还原反应合成受阻的z烯烃

  摘要：

  当在新的CC双键旁边有支链时，与氧化膦反应的Horner-Wittig反应的自然抗选择性降低。更好的方法是将相应的酮Luche还原成相应的酮，当将支链置于C上时具有较高的抗选择性。氧化膦旁的侧链。

  DOI：

  10.1016/0040-4039(95)01629-v

文献信息

• TiCl4 Mediated LiBH4 reduction of β-ketophosphine oxides: a high stereoselective route to the synthesis of anti-β-hydroxyphosphine oxides
  作者：Giuseppe Bartoli、Marcella Bosco、Letizia Sambri、Enrico Marcantoni

  DOI：10.1016/0040-4039(96)01601-2

  日期：1996.10

  The reduction of an α-alkyl-β-ketophosphine oxide with LiBH4 in presence of a strong chelating agent, such as TiCl4, gives the corresponding β-hydroxyphosphine oxide in high yields and with high anti-diastereoselectivity independently from the size of both the α- and β-alkyl chains.

  在强螯合剂（例如TiCl 4）存在下，用LiBH 4还原α-烷基-β-酮膦氧化物，可以独立于两者的大小，以高收率和高抗-非对映选择性生成相应的β-羟基膦氧化物。α-和β-烷基链。
• Opposite Stereochemical Effects Exerted by CeCl3 and TiCl4 on the Lewis Acid Mediated Reduction of α-Alkyl-β-ketophosphine Oxides with Metallic Hydrides: A Highly Stereoselective Protocol for the Synthesis of syn and anti α-alkyl-β-Hydroxyphosphine Oxides
  作者：Giuseppe Bartoli、Marcella Bosco、Letizia Sambri、Renato Dalpozzo、Enrico Marcantoni

  DOI：10.1002/chem.19970031209

  日期：1997.12

  AbstractA general, highly efficient methodology for obtaining both syn and anti β‐hydroxyphosphine oxides by reduction of the corresponding β‐ketophosphine oxides is described. The nature of the Lewis acid was found to be pivotal in determining the outcome of these reactions. Strongly chelating TiCl4 led to the anti isomer in high diastereoisomeric excess in noncoordinating solvents (CH2Cl2) at ‐78°C with BH3/py as reducing agent, while nonchelating CeCl3 gave a high excess of the syn isomer in coordinating solvents (THF) at the same temperature with LiBH4 as reducing agent. In the latter case, CeCl3 is essential in achieving high yields and stereoselectivity, since it allows the reaction to be performed at low temperatures. Otherwise, higher temperatures (0°C) are required, which lower both yields and selectivities. Moreover, each step of the protocol for the synthesis of stereodefined disubstituted olefins from alkylphosphine oxides (Warren's modification of the Horner procedure) has been optimized, and the optimized procedure has been applied to the synthesis of muscalure, the pheromone of the domestic fly.