| 1512803-41-6

• 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
• CAS: 1512803-41-6
• 化学式: C₁₂H₁₅O₅P
• 分子量: 270.222
• InChiKey: NRNXBZNNAVIYOU-CMDGGOBGSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.72
• 重原子数：
  18.0
• 可旋转键数：
  5.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.25
• 拓扑面积：
  72.83
• 氢给体数：
  1.0
• 氢受体数：
  4.0

反应信息

• 作为反应物：
  描述：

  、 三甲基硅烷化重氮甲烷 以 甲醇 、 正己烷 为溶剂， 反应 0.5h， 以38 mg的产率得到(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
• 作为产物：
  描述：

  苯膦酰二氯 在 吡啶 、 silver(I) acetate 、 palladium diacetate 、 sodium hydroxide 作用下， 以 1,4-二氧六环 、 乙醚 、 二氯甲烷 、 水 为溶剂， 反应 24.0h， 生成
  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