1,3-diphenyl-2-(diphenylphosphinoyl)propan-1-one | 73270-38-9

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 直链 1,3-二芳基丙烷
• 英文名称: 1,3-diphenyl-2-(diphenylphosphinoyl)propan-1-one
• 英文别名: 2-diphenylphosphoryl-1,3-diphenylpropan-1-one
• CAS: 73270-38-9
• 化学式: C₂₇H₂₃O₂P
• 分子量: 410.452
• InChiKey: LTQKTKITTDPXRK-UHFFFAOYSA-N

物化性质

• 熔点：
  208-210 °C(Solv: ethyl acetate (141-78-6); methanol (67-56-1); hexane (110-54-3))
• 沸点：
  574.0±50.0 °C(Predicted)
• 密度：
  1.20±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  5.49
• 重原子数：
  30.0
• 可旋转键数：
  7.0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.07
• 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：

  1,3-diphenyl-2-(diphenylphosphinoyl)propan-1-one 在 sodium tetrahydroborate 、 lithium aluminium tetrahydride 、 cerium(III) chloride 作用下， 以 四氢呋喃 、 乙醇 为溶剂， 反应 2.0h， 生成 (1RS,2RS)-1,3-diphenyl-2-(diphenylphosphinyl)propan-1-ol
  参考文献：
  名称：

  烯烃的合成通过外延鏻物种：1.一种抗-Wittig消除

  摘要：

  反-1,2-氧膦醇11和它们相应的顺式处理时-异构体与三氯化磷和三乙胺给予Ë和Ž分别烯烃，由抗消除。这与相应的1,2-膦酰基醇的合成的霍纳-维蒂希（Honer-Wittig）消除形成鲜明对比。通过用氯化铈（III）/氢化铝锂还原1，2-膦酰基醇来制备1，2-膦酰基醇11。通过消除瞬态表epi物种的形成来解释抗消除。意外的E描述了在氯化铈（III）/氢化铝锂还原期间，其中二苯基膦酰基与芳基相邻的1,2-膦酰基醇的-选择性Horner-Wittig消除。这导致了抗有丝分裂剂E -combretastatin A-4的合成。还描述了由相应的膦-硼烷配合物合成1，2-膦基醇的方法。

  DOI：

  10.1016/s0040-4020(98)00959-4
• 作为产物：
  描述：

  苯甲酸甲酯 在 正丁基锂 、 sodium methylate 作用下， 以 四氢呋喃 为溶剂， 反应 31.5h， 生成 1,3-diphenyl-2-(diphenylphosphinoyl)propan-1-one
  参考文献：
  名称：

  Diphenylphosphinoyl-mediated synthesis of ketones

  摘要：

  α-二苯基膦酰基酮在α位上选择性且顺序性地进行烷基化。双锂化和选择性烷基化发生在较不稳定的γ位。脱膦酰化得到的烷基化产物是酮。单烷基化具有选择性，形成的中间体晶体高度结晶，且可以进行一步完成的方法。该方法非常适合制备酸敏感的酮。

  DOI：

  10.1039/b606873a

文献信息

• Copper-catalyzed tandem phosphination–decarboxylation–oxidation of alkynyl acids with H-phosphine oxides: a facile synthesis of β-ketophosphine oxides
  作者：Pengbo Zhang、Liangliang Zhang、Yuzhen Gao、Jian Xu、Hua Fang、Guo Tang、Yufen Zhao

  DOI：10.1039/c5cc01904d

  日期：——

  The general method for the tandem phosphination–decarboxylation–oxidation of alkynyl acids under aerobic conditions has been developed.

  烯丙酸的串联磷化-脱羧-氧化反应的一般方法已经开发出来。
• 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。
• An efficient preparation of β-ketophosphine oxides from alkynylphosphine oxides with benzaldehyde oxime as a hydroxide source
  作者：Lu-Lu Chen、Jing-Wen Zhang、Wan-Wan Yang、Pei Chen、Dan-Yun Chen、Yan-Bo Wang

  DOI：10.1039/c9ob00251k

  日期：——

  An effective and facile transition-metal-free method has been developed for the synthesis of β-ketophosphine oxides from alkynylphosphine oxides with benzaldehyde oxime as a hydroxide surrogate. The current methodology provides simple access to various β-ketophosphine oxides in moderate to excellent yields with a broad substrate scope.

  已经开发了一种有效且简便的无过渡金属的方法，该方法以苯甲醛肟为氢氧化物替代物，从炔基膦氧化物合成β-酮膦氧化物。当前的方法可以轻松获得各种β-酮膦氧化物，具有中等范围到极好的收率，具有广泛的底物范围。
• 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.
• Torr, Richard S.; Warren, Stuart, Journal of the Chemical Society. Perkin transactions I, 1983, p. 1173 - 1180
  作者：Torr, Richard S.、Warren, Stuart

  DOI：——

  日期：——