diethyl (1,2-diphenylethyl)phosphonate | 33973-24-9

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 二苯乙烯类
• 英文名称: diethyl (1,2-diphenylethyl)phosphonate
• 英文别名: (2-diethoxyphosphoryl-2-phenylethyl)benzene
• CAS: 33973-24-9
• 化学式: C₁₈H₂₃O₃P
• 分子量: 318.353
• InChiKey: WFSCIJISRLWEGZ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.24
• 重原子数：
  22.0
• 可旋转键数：
  8.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  35.53
• 氢给体数：
  0.0
• 氢受体数：
  3.0

反应信息

• 作为反应物：
  描述：

  diethyl (1,2-diphenylethyl)phosphonate 生成 (+/-)-1,2-Diphenyl-aethylphosphonsaeure
  参考文献：
  名称：

  Benzylphosphonic acid inhibitors of human prostatic acid phosphatase

  摘要：

  A series of alpha-substituted benzylphosphonic acids is described as inhibitors of human prostatic acid phosphatase, an enzyme which has been used as a model to study aryl phosphatases. The most potent inhibitors in this series are 2-trifluoromethylbenzhydrylphosphonic acid (9 mu M), and alpha-(2-phenylethyl)benzylphosphonic acid (14 mu M) The structure-activity studies suggest that bulk tolerance beyond the phosphate binding area limits the steric or hydrophobic contribution to inhibitor potency achieved through alpha-carbon substitution.

  DOI：

  10.1016/0960-894x(96)00018-2
• 作为产物：
  描述：

  diethyl (E)-1,2-diphenylethenylphosphonate 在 (R,R)-(-)-2,3-bis(tert-butylmethylphosphino)benzene 、 氢气 、 nickel(II) acetate tetrahydrate 作用下， 以 2,2,2-三氟乙醇 为溶剂， 40.0 ℃ 、3.0 MPa 条件下， 以95%的产率得到
  参考文献：
  名称：

  镍催化α-取代乙烯基膦酸酯和二芳基乙烯基膦氧化物的不对称氢化

  摘要：

  开发了第一个使用 H 2对末端烯烃进行有效的镍催化不对称氢化反应，提供了高达 99% 收率、96% ee 和 1000 S/C（底物/催化剂）的手性乙基膦产物。计算和实验机理研究表明，产物中加入的两个氢原子来源于H 2，反应通过Ni II而不是Ni 0循环过程进行。

  DOI：

  10.1002/anie.202214990

文献信息

• Mild Synthesis of Organophosphorus Compounds:  Reaction of Phosphorus-Containing Carbenoids with Organoboranes
  作者：Monika I. Antczak、Jean-Luc Montchamp

  DOI：10.1021/ol800085u

  日期：2008.3.1

  Organoboranes react with phosphorus-containing carbenoids to produce a variety of functionalized organophosphorus compounds under mild conditions. In some cases, selective migration of one group attached to boron can be observed. Phosphonite-borane complexes are introduced as novel synthons for the synthesis of phosphinic esters.

  有机硼烷在温和条件下与含磷类卡宾反应生成多种功能化的有机磷化合物。在某些情况下，可以观察到与硼相连的一组选择性迁移。次膦酸酯-硼烷复合物被引入作为合成次膦酸酯的新型合成子。
• Catalytic Dibenzocyclooctene Synthesis via Cobalt(III)-Carbene Radical and <i>ortho</i> -Quinodimethane Intermediates
  作者：Colet te Grotenhuis、Naudin van den Heuvel、Jarl Ivar van der Vlugt、Bas de Bruin

  DOI：10.1002/anie.201711028

  日期：2018.1.2

  non‐innocent carbene intermediate. This method offers a novel route to prepare eight‐membered rings, using base metal catalysis to construct a series of unique dibenzocyclooctenes through selective Ccarbene−Caryl cyclization. The desired eight‐membered‐ring products were obtained in good to excellent yields. A large variety of aromatic substituents are tolerated. The proposed reaction mechanism involves intramolecular

  以[Co(TPP)]（TPP=四苯基卟啉）为催化剂对邻苯甲基芳基N-甲苯磺酰腙进行金属自由基活化，使得能够控制地利用氧化还原非无害卡宾中间体的单电子反应性。该方法提供了一种制备八元环的新途径，利用贱金属催化，通过选择性C碳烯-C芳基环化构建一系列独特的二苯并环辛烯。以良好至优异的收率获得了所需的八元环产物。可以耐受多种芳香族取代基。所提出的反应机制涉及分子内氢原子转移（HAT）到Co III -卡宾自由基中间体，然后解离经历8π环化的邻醌二甲烷。该机制得到了 DFT 计算的支持，并且自由基型中间体的存在通过捕获实验得到了证实。
• Benzylphosphonic acid inhibitors of human prostatic acid phosphatase
  作者：Charles F. Schwender、Scott A. Beers、Elizabeth A. Malloy、Jacqueline J. Cinicola、David J. Wustrow、Keith D. Demarest、Jerold Jordan

  DOI：10.1016/0960-894x(96)00018-2

  日期：1996.2

  A series of alpha-substituted benzylphosphonic acids is described as inhibitors of human prostatic acid phosphatase, an enzyme which has been used as a model to study aryl phosphatases. The most potent inhibitors in this series are 2-trifluoromethylbenzhydrylphosphonic acid (9 mu M), and alpha-(2-phenylethyl)benzylphosphonic acid (14 mu M) The structure-activity studies suggest that bulk tolerance beyond the phosphate binding area limits the steric or hydrophobic contribution to inhibitor potency achieved through alpha-carbon substitution.
• Nickel‐Catalyzed Asymmetric Hydrogenation of α‐Substituted Vinylphosphonates and Diarylvinylphosphine Oxides
  作者：Hanlin Wei、Hao Chen、Jianzhong Chen、Ilya D. Gridnev、Wanbin Zhang

  DOI：10.1002/anie.202214990

  日期：2023.2

  The first efficient Ni-catalyzed asymmetric hydrogenation of terminal olefins using H2 was developed, affording chiral ethylphosphine products with up to 99 % yield, 96 % ee and 1000 S/C (substrate/catalyst). The calculation and experimental mechanism study indicate that the two added hydrogen atoms of the product originate from H2 and the reaction proceeds through a NiII rather than Ni0 cyclic process

  开发了第一个使用 H 2对末端烯烃进行有效的镍催化不对称氢化反应，提供了高达 99% 收率、96% ee 和 1000 S/C（底物/催化剂）的手性乙基膦产物。计算和实验机理研究表明，产物中加入的两个氢原子来源于H 2，反应通过Ni II而不是Ni 0循环过程进行。