diethyl (2-(p-methylphenyl)prop-1(E)-enyl)phosphonate

• 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: diethyl (2-(p-methylphenyl)prop-1(E)-enyl)phosphonate
• 英文别名: (E)-diethyl (2-(p-tolyl)prop-1-en-1-yl)phosphonate；diethyl (E)-(2-(4-tolyl)prop-1-en-1-yl)phosphonate；diethyl (E)-(2-(p-tolyl)prop-1-en-1-yl)phosphonate；(E)-diethyl 2-(4-methylphenyl)prop-1-enylphosphonate；1-[(E)-1-diethoxyphosphorylprop-1-en-2-yl]-4-methylbenzene
• 化学式: C₁₄H₂₁O₃P
• 分子量: 268.293
• InChiKey: DXOUVRHVIQCAKS-ACCUITESSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.2
• 重原子数：
  18
• 可旋转键数：
  6
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.43
• 拓扑面积：
  35.5
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  diethyl (2-(p-methylphenyl)prop-1(E)-enyl)phosphonate 在 bis(1,5-cyclooctadiene)rhodium(I) tetrafluoroborate 、 (R)-1-{(R)-2-(2'-diphenylphosphinophenyl)ferrocenyl}ethyldi(3,5-xylyl)phosphine 、 蒽 、 氢气 作用下， 以 二氯甲烷 、 乙腈 为溶剂， 20.0 ℃ 、1.0 MPa 条件下， 反应 42.0h， 生成 diethyl (S)-(2-(4-tolyl)propyl)phosphonate
  参考文献：
  名称：

  通过选择性能量转移催化转化外部不对称感应：β-手性膦酸盐对映体的策略。

  摘要：

  对映体，催化还原的活化烯烃将对映手性催化剂中编码的立体化学信息传递给前手性底物。尽管该策略很有效，但仍然容易受到两种催化剂对映体的成本和来源的困扰。本文中，公开了使用催化剂的单一对映异构体的α，β-不饱和膦酸酯的立体发散氢化。这使得能够以相等和相反的选择性产生R-或S-构型的β-手性膦酸酯。通过容易的E→Z异构化的发展，在底物水平上调节对映发散。通过使用蒽作为廉价的有机光敏剂进行选择性的能量转移催化，首次实现了这一点。本身具有综合价值，该过程使得随后的RhI介导的立体有择加氢反应仅使用S催化剂即可生成产物的两种对映异构体（最高达99：1和3:97 er）。该策略胜过了使用E底物和R催化剂观察到的选择性。

  DOI：

  10.1002/anie.201911651
• 作为产物：
  描述：

  (E)-1-methyl-4-(1-nitroprop-1-en-2-yl)benzene 、 亚磷酸二乙酯 在 nickel(II) nitrate hexahydrate 、 silver nitrate 作用下， 以 乙腈 为溶剂， 反应 12.0h， 以79%的产率得到diethyl (2-(p-methylphenyl)prop-1(E)-enyl)phosphonate
  参考文献：
  名称：

  Ag(I)-catalyzed synthesis of (E)-alkenyl phosphonates by oxidative coupling of H-phosphites with β-nitroolefins

  摘要：

  DOI：

  10.1016/j.tetlet.2021.153530

文献信息

• Palladium(0)-Catalyzed Highly Regio- and Stereoselective Addition of Organoboronic Acids with 1,2-Allenylphosphonates Forming Tri- or Tetrasubstituted 1(<i>E</i>)-Alkenylphosphonates
  作者：Shengming Ma、Hao Guo、Fei Yu

  DOI：10.1021/jo060672t

  日期：2006.8.1

  A highly regio- and stereoselective palladium(0)-catalyzed addition of organoboronic acids with 1,2-allenylphosphonates in the presence of HOAc forming tri- or tetrasubstituted 1(E)-alkenylphosphonates is reported in this paper. The stereoselectivity is much higher than the reported cases. The effects of different R1, R2, and R3 were studied. A mechanism of this reaction is proposed on the basis of

  本文报道了在HOAc的存在下，高区域选择性和立体选择性钯（0）催化的有机硼酸与1,2-烯基膦酸酯的加成反应，形成三或四取代的1（E）-烯基膦酸酯。立体选择性远高于报道的情况。研究了不同的R 1，R 2和R 3的影响。在我们以前的研究的基础上，提出了这种反应的机理。
• Enantioselective Synthesis of Chiral Phosphonates via Rh/f-spiroPhos Catalyzed Asymmetric Hydrogenation of β,β-Disubstituted Unsaturated Phosphonates
  作者：Chaoqiong Wang、Fang Xie、Qianling Guo、Chaochao Xie、Guofu Zi、Weiping Ye、Zhangtao Zhou、Guohua Hou、Zhanbin Zhang

  DOI：10.1021/acs.joc.1c01397

  日期：2021.9.3

  The first asymmetric hydrogenation of β,β-diaryl unsaturated phosphonates has been realized for synthesis of β,β-diaryl chiral phosphonates with excellent enantioselectivities (up to 99.9% ee) catalyzed by the Rh-(R,R)-f-spiroPhos complex. Furthermore, this catalyst also exhibits comparably excellent performance for β-aryl-β-alkyl unsaturated phosphonates providing the corresponding chiral phosphonates

  首次实现了β,β-二芳基不饱和膦酸酯的不对称氢化，用于在Rh-( R , R )-f-spiroPhos 络合物催化下合成具有优异对映选择性（高达99.9% ee）的β,β-二芳基手性膦酸酯. 此外，该催化剂对 β-芳基-β-烷基不饱和膦酸酯也表现出相当优异的性能，提供相应的手性膦酸酯，其 ee 值高达 99.9%。这种方法为不对称合成手性膦酸盐提供了一种直接的途径。
• Enantioselective Synthesis of Optically Active Alkanephos- phonates<i>via</i>Rhodium-Catalyzed Asymmetric Hydrogenation of β-Substituted α,β-Unsaturated Phosphonates with Ferrocene-Based Monophosphoramidite Ligands
  作者：Zheng-Chao Duan、Xiang-Ping Hu、Dao-Yong Wang、Jia-Di Huang、Sai-Bo Yu、Jun Deng、Zhuo Zheng

  DOI：10.1002/adsc.200800388

  日期：2008.9.5

  series of chiral β-substituted alkanephosphonates was synthesized in high enantioselectivities via the first rhodium-catalyzed asymmetric hydrogenation of the corresponding β-substituted-α,β-unsaturated phosphonates using a ferrocene-derived monophosphoramidite ligand, with which up to 99.5% ee have been achieved for the hydrogenation of (E)-substrates and 98.0% ee for (Z)-substrates.

  一系列手性β取代alkanephosphonates的是在高对映选择性合成经由相应的β取代-α的第一铑催化的不对称氢化，β不饱和膦酸酯用二茂铁衍生monophosphoramidite配体，利用该高达99.5％ee值有无（E）底物的氢化反应达到了氢化，（Z）底物的氢化反应达到了98.0％ee。
• Enantioselective synthesis of optically active alkylphosphonates via Rh-catalyzed asymmetric hydrogenation of β-substituted α,β-unsaturated phosphonates
  作者：Zheng-chao Duan、Lian-zhi Wang、Xin-jian Song、Xiang-ping Hu、Zhuo Zheng

  DOI：10.1016/j.tetasy.2012.03.024

  日期：2012.4

  The Rh-catalyzed asymmetric hydrogenation of beta-substituted alpha,beta-unsaturated phosphonates using (S-c,S-p)-WalPhos as the chiral ligand is reported, in which a wide range of optically active beta-substituted alkylphosphonates were obtained in good yields and with good to excellent enantioselectivities (86-98% ee). In contrast to the Rh/(R-c,S-a)-FAPhos system previously reported by us, the present catalytic system shows a wider substrate scope, and can perform the hydrogenation under milder reaction conditions. Crown Copyright (C) 2012 Published by Elsevier Ltd. All rights reserved.
• Rhodium-Catalyzed Enantioselective Hydrogenation of Unsaturated Phosphonates by ClickFerrophos Ligands
  作者：Takashi Konno、Kenta Shimizu、Kenichi Ogata、Shin-ichi Fukuzawa

  DOI：10.1021/jo300129m

  日期：2012.4.6

  Newly developed ClickFerrophos II ligands were applied in the hydrogenation of alpha,beta-unsaturated phosphonates. The use of a rhodium/ClickFerrophos II catalyst was examined in the hydrogenation of fimctionalized alpha,beta-unsaturated phosphonates and was revealed to be effective for beta-alkyl-beta-aryl or beta-dialkyl phosphonates, (Z)-beta-enolester phosphonates, and alpha-phenylethenyl phosphonates, producing the corresponding chiral phosphonates in good yields with high enantioselectivities (up to 96% ee).