diethyl 1-[hydroxy(phenyl)methyl]vinylphosphonate | 213193-52-3

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 有机膦酸及其衍生物
• 英文名称: diethyl 1-[hydroxy(phenyl)methyl]vinylphosphonate
• 英文别名: 2-Diethoxyphosphoryl-1-phenylprop-2-en-1-ol
• CAS: 213193-52-3
• 化学式: C₁₃H₁₉O₄P
• 分子量: 270.265
• InChiKey: ZKGGEGJBQKUBDE-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.5
• 重原子数：
  18
• 可旋转键数：
  7
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.38
• 拓扑面积：
  55.8
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  diethyl 1-[hydroxy(phenyl)methyl]vinylphosphonate 在 三氯化铁 、 三苯基膦 作用下， 以 1,4-二氧六环 、 乙腈 为溶剂， 反应 3.0h， 生成 5,6-Dichloro-2-(2-diethoxyphosphoryl-1-phenylprop-2-enyl)isoindole-1,3-dione
  参考文献：
  名称：

  Phosphine-Catalyzed Allylic Substitution of Morita−Baylis−Hillman Acetates:  Synthesis of N-Protected β-Aminophosphonic Acid Esters

  摘要：

  A series of N-protected beta-amino phosphonic acid esters have been prepared by phosphine-catalyzed allylic substitution of 2-(diethylphosphonyl)-substituted allylic acetates employing 4,5-dichlorophthalimide as nucleophilic partner. These organocatalytic allylic substitutions exhibit exceptionally high levels of regiospecificity by virtue of a tandem S(N)2'-S(N)2' mechanism.

  DOI：

  10.1021/jo061218s
• 作为产物：
  描述：

  tert-butyl (2-(diethoxyphosphoryl)-1-phenylallyl) carbonate 在 三乙烯二胺 、 水 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 7.5h， 以76%的产率得到diethyl 1-[hydroxy(phenyl)methyl]vinylphosphonate
  参考文献：
  名称：

  Lewis Base Catalyzed Enantioselective Allylic Hydroxylation of Morita–Baylis–Hillman Carbonates with Water

  摘要：

  A Lewis base catalyzed allylic hydroxylation of Morita-Baylis-Hillman (MBH) carbonates has been developed. Various chiral MBH alcohols can be synthesized in high yields (up to 99%) and excellent enantioselectivities (up to 94% ee). This is the first report using water as a nucleophile in asymmetric organocatalysis. The nucleophilic role of water has been verified using O-18-labeling experiments.

  DOI：

  10.1021/jo201096e

文献信息

• Synthesis of Morita–Baylis–Hillman-fluorides using 1,1,2,2-tetrafluoroethyl-N,N-dimethylamine
  作者：Yuji Sumii、Takato Nagasaka、Ayaka Matsuno、Hidetoshi Hayashi、Hideyuki Mimura、Takumi Kagawa、Norio Shibata

  DOI：10.1016/j.tet.2021.132387

  日期：2021.9

  platforms for asymmetric allylic substitution reactions. However, the preparation of MBH-fluorides requires the use of an explosive fluorinating reagent, namely (diethylamino)sulfur trifluoride (DAST). Thus, we herein report a safe, alternative method for the preparation of MBH-fluorides via the deoxyfluorination of MBH-alcohols using 1,1,2,2-tetrafluoroethyl-N,N-dimethylamine (TFEDMA). Accordingly, a

  Morita-Baylis-Hillman (MBH)-氟化物是不对称烯丙基取代反应的宝贵平台。然而，MBH-氟化物的制备需要使用爆炸性氟化试剂，即（二乙氨基）三氟化硫（DAST）。因此，我们在此报告了一种安全的替代方法，通过使用 1,1,2,2-四氟乙基-N , N-二甲胺 (TFEDMA)对 MBH-醇进行脱氧氟化来制备 MBH-氟化物。因此，在不需要活化剂的情况下，各种 MBH-醇以中等至良好的产率顺利转化为其相应的 MBH-氟化物。发现该氟化反应通过涉及稳定烯丙基阳离子中间体的 S N 1 过程进行。
• Huang, Bin; Sheng, Shou-Ri; Huang, Yi-Xiang, Journal of Chemical Research, 2006, # 10, p. 623 - 625
  作者：Huang, Bin、Sheng, Shou-Ri、Huang, Yi-Xiang、Xin, Qin、Song, Li-Yan、Luo, Nian-Hua

  DOI：——

  日期：——
• Lewis Base Catalyzed Enantioselective Allylic Hydroxylation of Morita–Baylis–Hillman Carbonates with Water
  作者：Bo Zhu、Lin Yan、Yuanhang Pan、Richmond Lee、Hongjun Liu、Zhiqiang Han、Kuo-Wei Huang、Choon-Hong Tan、Zhiyong Jiang

  DOI：10.1021/jo201096e

  日期：2011.8.19

  A Lewis base catalyzed allylic hydroxylation of Morita-Baylis-Hillman (MBH) carbonates has been developed. Various chiral MBH alcohols can be synthesized in high yields (up to 99%) and excellent enantioselectivities (up to 94% ee). This is the first report using water as a nucleophile in asymmetric organocatalysis. The nucleophilic role of water has been verified using O-18-labeling experiments.
• Phosphine-Catalyzed Allylic Substitution of Morita−Baylis−Hillman Acetates:  Synthesis of N-Protected β-Aminophosphonic Acid Esters
  作者：HaeIl Park、Chang-Woo Cho、Michael J. Krische

  DOI：10.1021/jo061218s

  日期：2006.9.1

  A series of N-protected beta-amino phosphonic acid esters have been prepared by phosphine-catalyzed allylic substitution of 2-(diethylphosphonyl)-substituted allylic acetates employing 4,5-dichlorophthalimide as nucleophilic partner. These organocatalytic allylic substitutions exhibit exceptionally high levels of regiospecificity by virtue of a tandem S(N)2'-S(N)2' mechanism.