E-1-carbethoxy-1-diethoxyphosphoryl-2-(2-chlorophenyl) ethene | 53235-78-2

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 肉桂酸及其衍生物
• 英文名称: E-1-carbethoxy-1-diethoxyphosphoryl-2-(2-chlorophenyl) ethene
• 英文别名: Ethyl 3-(2-chlorophenyl)-2-(diethoxyphosphoryl)acrylate；ethyl (E)-3-(2-chlorophenyl)-2-diethoxyphosphorylprop-2-enoate
• CAS: 53235-78-2
• 化学式: C₁₅H₂₀ClO₅P
• 分子量: 346.748
• InChiKey: LBNOGAOWELCLMX-SDNWHVSQSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.2
• 重原子数：
  22
• 可旋转键数：
  9
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.4
• 拓扑面积：
  61.8
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  E-1-carbethoxy-1-diethoxyphosphoryl-2-(2-chlorophenyl) ethene 、 Phenyl-methanesulfonic acid (3aR,5R,6R,6aR)-5-((R)-2,2-dimethyl-[1,3]dioxolan-4-yl)-2,2-dimethyl-tetrahydro-furo[2,3-d][1,3]dioxol-6-yl ester 在 正丁基锂 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 反应 5.0h， 以96%的产率得到
  参考文献：
  名称：

  Efficient diastereo- and enantioselective synthesis of α,β-disubstituted γ-phosphono sulfonates

  摘要：

  The first asymmetric synthesis of alpha,beta-disubstituted gamma-phosphono sulfonates is reported. The key step is the Michael addition of a lithiated enantiopure sulfonate bearing an inexpensive chiral sugar auxiliary to alpha,beta-unsaturated phosphonates in good diastereoselectivities. After chromatographic purification, the cleavage of the chiral sugar auxiliary proceeds without any epimerization or racemization to form the corresponding isopropyl sulfonate in very good overall yield (75%) and excellent diastereomeric and enantiomeric excess (de, ee >= 95%). (C) 2009 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetasy.2009.10.011
• 作为产物：
  描述：

  2-溴-2-磷酰基乙酸三乙酯 、 2-氯苯甲醛 在 三丁基砷 作用下， 反应 14.0h， 以85%的产率得到E-1-carbethoxy-1-diethoxyphosphoryl-2-(2-chlorophenyl) ethene
  参考文献：
  名称：

  A Highly Stereoselective Synthesis of α-Carbethoxy-α,β-unsaturated Phosphonates Mediated by Tri-n-Butylarsine

  摘要：

  A highly stereoselective synthesis of alpha-carbethoxy-alpha,beta-unsaturated phosphonates in 71-92% yield mediated by tri-n-butylarsine under neutral condition is described.

  DOI：

  10.1080/00397919308011152

文献信息

• Knoevenagel kondensationen mit TiCl4/base-IV
  作者：W. Lehnert

  DOI：10.1016/s0040-4020(01)91461-9

  日期：1974.1

  In the presence of titanium tetrachloride and an organic base in tetrahydrofurane, triethyl phosphonoacetic acid undergoes condensation with aliphatic and aromatic aldehydes and aromatic ketones to yield the corresponding triethyl alkylidene and arylidene phosphonoacetic acids respectively. Tetraalkyl methylenediphosphonates and aromatic or aliphatic α-branched aldehydes react under identical conditions

  在四氯化钛和有机碱在四氢呋喃中的存在下，三乙基膦酰基乙酸与脂族和芳族醛和芳族酮缩合，分别得到相应的三乙基亚烷基和亚芳基膦酰基乙酸。亚甲基二膦酸四烷基酯与芳族或脂族α-支化醛在相同条件下以相同方式反应。众所周知的三乙基亚烷基和亚芳基膦酰基乙酸以及新的四烷基亚烷基和亚芳基甲烷二膦酸很容易在乙醇中催化或通过硼氢化钠加氢，以几乎定量的产率得到相应的饱和化合物。
• Enantioselective Michael addition to vinyl phosphonates <i>via</i> hydrogen bond-enhanced halogen bond catalysis
  作者：Mikk Kaasik、Jevgenija Martõnova、Kristin Erkman、Andrus Metsala、Ivar Järving、Tõnis Kanger

  DOI：10.1039/d1sc01029h

  日期：——

  malononitrile to vinyl phosphonates was accomplished by hydrogen bond-enhanced bifunctional halogen bond (XB) catalysis. NMR titration experiments were used to demonstrate that halogen bonding, with the support of hydrogen-bonding, played a key role in the activation of the Michael acceptors through the phosphonate group. This is the first example of the use of XBs for the activation of organophosphorus

  丙二腈与乙烯基膦酸酯的不对称迈克尔加成是通过氢键增强的双官能卤键（XB）催化完成的。核磁共振滴定实验证明，卤素键在氢键的支持下，在通过膦酸酯基团激活迈克尔受体方面发挥了关键作用。这是在合成过程中使用 XB 来活化有机磷化合物的第一个例子。此外，碘代全氟苯基被证明是比不同的碘代和硝基取代的苯基更好的定向单元。所开发的方法提供了具有优异产率和非对映选择性以及良好对映选择性的产品。
• Efficient diastereo- and enantioselective synthesis of α,β-disubstituted γ-phosphono sulfonates
  作者：Dieter Enders、Zohreh Mirjafary、Hamdollah Saeidian

  DOI：10.1016/j.tetasy.2009.10.011

  日期：2009.11

  The first asymmetric synthesis of alpha,beta-disubstituted gamma-phosphono sulfonates is reported. The key step is the Michael addition of a lithiated enantiopure sulfonate bearing an inexpensive chiral sugar auxiliary to alpha,beta-unsaturated phosphonates in good diastereoselectivities. After chromatographic purification, the cleavage of the chiral sugar auxiliary proceeds without any epimerization or racemization to form the corresponding isopropyl sulfonate in very good overall yield (75%) and excellent diastereomeric and enantiomeric excess (de, ee >= 95%). (C) 2009 Elsevier Ltd. All rights reserved.
• A Highly Stereoselective Synthesis of α-Carbethoxy-α,β-unsaturated Phosphonates Mediated by Tri-n-Butylarsine
  作者：Yanchang Shen、Baozhen Yang

  DOI：10.1080/00397919308011152

  日期：1993.12

  A highly stereoselective synthesis of alpha-carbethoxy-alpha,beta-unsaturated phosphonates in 71-92% yield mediated by tri-n-butylarsine under neutral condition is described.