3-(diphenylphosphinoyl)cyclopentanone | 455310-87-9

• 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: 3-(diphenylphosphinoyl)cyclopentanone
• 英文别名: 3-(diphenylphosphoryl)cyclopentanone；3-(diphenylphosphinoxy)cyclopentanone；3-Diphenylphosphorylcyclopentan-1-one；3-diphenylphosphorylcyclopentan-1-one
• CAS: 455310-87-9
• 化学式: C₁₇H₁₇O₂P
• 分子量: 284.295
• InChiKey: QWHBCMKWQPDTLT-UHFFFAOYSA-N

物化性质

• 熔点：
  204.5-205.5 °C
• 沸点：
  424.5±38.0 °C(Predicted)
• 密度：
  1.20±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.4
• 重原子数：
  20
• 可旋转键数：
  3
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.24
• 拓扑面积：
  34.1
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  3-(diphenylphosphinoyl)cyclopentanone 在 sodium tetrahydroborate 作用下， 以 甲醇 为溶剂， 反应 19.0h， 生成 trans-3-(diphenylphosphinoyl)cyclopentanol 、 cis-3-(diphenylphosphinoyl)cyclopentanol
  参考文献：
  名称：

  Towards chiral non-racemic cis -1,3-disubstituted cyclopentane 1,4-diphosphines

  摘要：

  Reaction of dialkyl- or diaryl-trans-(3,4-epoxycyclopentyl)phosphine oxides 2 with the lithium derivative of methyldiphenylphosphine oxide gives a mixture of (+/-)-t-4- and (+/-)-c-4-(disubstituted phosphinoyl)-t-2-(diphenylphosphinoyl-methyl)-r-1-cyclopentanol derivatives 13a-c and 16a-c, which could be obtained in pure form by separation of the corresponding acetates 14a-c and 17a-c followed by methanolysis. Compounds 13b and 16b were transformed into the corresponding dehydroxy derivatives 19 and 21 through the Barton procedure. Additionally, 16a was transformed into a diastereomeric mixture of carbamates 22 and 23 on reaction with (S)-alpha-phenylethylisocyanate which could be separated by repeated crystallization. The relative configuration of compounds 13b, 17a, 21 and 22 was established by X-ray diffraction analysis. (C) 2002 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0957-4166(02)00184-2
• 作为产物：
  描述：

  triisopropylsilyldiphenylphosphine 在 [(dppp)Rh(cod)]⁺ClO₄^- 1,3-双(二苯基膦)丙烷 、 双氧水 、 三乙胺 作用下， 以 1,4-二氧六环 、 水 、 乙酸乙酯 为溶剂， 反应 52.0h， 生成 3-(diphenylphosphinoyl)cyclopentanone
  参考文献：
  名称：

  铑（i）催化的环状α，β-不饱和酮的共轭磷酸化与甲硅烷基膦作为掩蔽的次膦化物。

  摘要：

  甲硅烷基膦中磷（iii）-硅键的亲核活化产生亲核性磷（iii）等效物，从而允许铑催化的β-取代的α，β-不饱和受体的共轭磷化。

  DOI：

  10.1039/b706137d

文献信息

• Conjugate phosphination of cyclic and acyclic acceptors using Rh(I)–phosphine or Rh(I)–carbene complexes. Probing the mechanism with chirality at the silicon atom or the phosphorus atom of the Si–P reagent
  作者：Verena T. Trepohl、Roland Fröhlich、Martin Oestreich

  DOI：10.1016/j.tet.2009.04.038

  日期：2009.8

  The Rh(I)-catalyzed conjugate phosphinyl transfer from an Si–P reagent to an electron-deficient acceptor requires individual protocols for cyclic and acyclic α,β-unsaturated carbonyls and carboxyls. While 1,4-addition to cyclic acceptors is catalyzed by a Rh(I)–phosphine complex, a Rh(I)–carbene complex is needed to promote conjugate phosphination of acyclic acceptors. General procedures for both systems

  从Si-P试剂到缺电子受体的Rh（I）催化的共轭亚膦酰基转移需要针对环状和非环状α，β-不饱和羰基和羧基的单独方案。尽管Rh（I）-膦配合物可催化向环受体加成1,4-，但需要Rh（I）-卡宾配合物来促进非环受体的共轭磷酸化。报告了这两个系统的一般步骤。除了单膦源化的Si-P试剂作为次膦化物来源外，具有两个Si-P单元的dppe-以及dppp衍生的试剂也参与了该反应。这种Rh（I）催化Si-P试剂活化的机制仍在争论中。使用对映纯硅立体异构和外消旋磷立体异构Si-P试剂进行的对照实验支持催化从重金属化而不是氧化加成开始。包括本研究中使用的Si-P化合物的制备和全部表征数据。
• P–C Bond formation via direct and three-component conjugate addition catalyzed by 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD)
  作者：Zhiyong Jiang、Yan Zhang、Weiping Ye、Choon-Hong Tan

  DOI：10.1016/j.tetlet.2006.11.019

  日期：2007.1

  The direct addition of P(O)–H bonds (dialkyl phosphites and diphenyl phosphonite) across various activated alkenes was catalyzed effectively by 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD). This is a mild, rapid and efficient protocol to generate P–C bonds. This simple procedure allows a series of dialkyl alkylphosphonates and trisubstituted phosphine oxides to be prepared in high yields. Further investigation

  1,5,7-三氮杂双环[4.4.0]癸-5-烯（TBD）有效地催化了各种活化烯烃之间直接添加的P（O）-H键（亚磷酸二烷基酯和亚磷酸二苯酯）。这是生成P–C键的温和，快速且有效的协议。这种简单的方法可以高收率制备一系列的烷基二膦酸烷基酯和三取代的氧化膦。进一步的研究导致了方便的一锅三组分反应，该反应包含二苯基亚膦酸酯，丙二腈和醛。
• Palladium(II)-Catalyzed Conjugate Phosphination of Electron-Deficient Acceptors
  作者：Verena T. Trepohl、Susumu Mori、Kenichiro Itami、Martin Oestreich

  DOI：10.1021/ol8028466

  日期：2009.3.5

  A general protocol for the conjugate transfer of diphenyl-, dicyclohexyl-, and di-tert-butylphosphinyl groups from silylphosphlnes to cyclic and acyclic electron-deficient acceptors employing a bench-stable palladium(II) catalyst Is reported. Several E and Z configured alpha,beta-unsaturated carbonyl and carboxyl acceptors (including imides) as well as nitroalkenes participate in this palladium(II)-catalyzed process in high chemical yields.