(E)-ethyl 3-(2-(dimethoxyphosphoryl)phenyl)acrylate | 1464720-99-7

• 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)-ethyl 3-(2-(dimethoxyphosphoryl)phenyl)acrylate
• 英文别名: ethyl (E)-3-(2-dimethoxyphosphorylphenyl)prop-2-enoate
• CAS: 1464720-99-7
• 化学式: C₁₃H₁₇O₅P
• 分子量: 284.249
• InChiKey: UWDYLJISSRIXES-MDZDMXLPSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.7
• 重原子数：
  19
• 可旋转键数：
  7
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.31
• 拓扑面积：
  61.8
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为产物：
  描述：

  苯基氯膦酸甲酯 在 silver(I) acetate 、 palladium diacetate 、 sodium hydroxide 作用下， 以 1,4-二氧六环 、 甲醇 、 正己烷 、 二氯甲烷 、 水 为溶剂， 反应 24.5h， 生成 (E)-ethyl 3-(2-(dimethoxyphosphoryl)phenyl)acrylate
  参考文献：
  名称：

  Double Role of the Hydroxy Group of Phosphoryl in Palladium(II)-Catalyzed ortho-Olefination: A Combined Experimental and Theoretical Investigation

  摘要：

  Density functional theory calculations have been carried out on Pd-catalyzed phosphoryl-directed ortho-olefination to probe the origin of the significant reactivity difference between methyl hydrogen benzylphosphonates and dimethyl benzylphosphonates. The overall catalytic cycle is found to include four basic steps: C-H bond activation, transmetalation, reductive elimination, and recycling of catalyst, each of which is constituted from different steps. Our calculations reveal that the hydroxy group of phosphoryl plays a crucial role almost in all steps, which can not only stabilize the intermediates and transition states by intramolecular hydrogen bonds but also act as a proton donor so that the eta(1)-CH3COO- ligand could be protonated to form a neutral acetic acid for easy removal. These findings explain why only the methyl hydrogen benzylphosphonates and methyl hydrogen phenylphosphates were found to be suitable reaction partners. Our mechanistic findings are further supported. by theoretical prediction of Pd-catalyzed ortho-olefination using methyl hydrogen phenylphosphonate, which is verified by experimental observations that the desired product was formed in a moderate yield.

  DOI：

  10.1021/jo402307x

文献信息

• Rhodium(iii)-catalyzed ortho-olefination of aryl phosphonates
  作者：Bathoju Chandra Chary、Sunggak Kim

  DOI：10.1039/c3ob41548a

  日期：——

  Rhodium(III)-catalyzed C–H olefination of aryl phosphonic esters is reported for the first time. In this mild and efficient process, the phosphonic ester group is utilized successfully as a new directing group. In addition, mono-olefination for aryl phosphonates is observed using a phosphonic diamide directing group.

  首次报道了铑（III）催化的芳基膦酸酯的CH H烯化反应。在这种温和而有效的过程中，膦酸酯基已成功用作新的导向基团。另外，使用膦二酰胺引导基团观察到芳基膦酸酯的单烯烃化。
• Double Role of the Hydroxy Group of Phosphoryl in Palladium(II)-Catalyzed <i>ortho</i>-Olefination: A Combined Experimental and Theoretical Investigation
  作者：Liu Leo Liu、Hang Yuan、Tingting Fu、Tao Wang、Xiang Gao、Zhiping Zeng、Jun Zhu、Yufen Zhao

  DOI：10.1021/jo402307x

  日期：2014.1.3

  Density functional theory calculations have been carried out on Pd-catalyzed phosphoryl-directed ortho-olefination to probe the origin of the significant reactivity difference between methyl hydrogen benzylphosphonates and dimethyl benzylphosphonates. The overall catalytic cycle is found to include four basic steps: C-H bond activation, transmetalation, reductive elimination, and recycling of catalyst, each of which is constituted from different steps. Our calculations reveal that the hydroxy group of phosphoryl plays a crucial role almost in all steps, which can not only stabilize the intermediates and transition states by intramolecular hydrogen bonds but also act as a proton donor so that the eta(1)-CH3COO- ligand could be protonated to form a neutral acetic acid for easy removal. These findings explain why only the methyl hydrogen benzylphosphonates and methyl hydrogen phenylphosphates were found to be suitable reaction partners. Our mechanistic findings are further supported. by theoretical prediction of Pd-catalyzed ortho-olefination using methyl hydrogen phenylphosphonate, which is verified by experimental observations that the desired product was formed in a moderate yield.