Methyl 3-(dimethoxyphosphoryl)but-3-enoate | 232927-73-0

• 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: Methyl 3-(dimethoxyphosphoryl)but-3-enoate
• 英文别名: methyl 3-dimethoxyphosphorylbut-2-enoate；Methyl 3-dimethoxyphosphorylbut-3-enoate
• CAS: 232927-73-0
• 化学式: C₇H₁₃O₅P
• 分子量: 208.151
• InChiKey: OFPLVCDRJGASQT-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -0.2
• 重原子数：
  13
• 可旋转键数：
  6
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.57
• 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：

  Methyl 3-(dimethoxyphosphoryl)but-3-enoate 在 bis(1,5-cyclooctadiene)rhodium(I) tetrafluoroborate 、 (2S,4S)-4-二苯基膦-2-(二苯基膦甲基)-N-叔丁氧羰基-吡咯烷 氢气 作用下， 以 甲醇 为溶剂， 25.0 ℃ 、100.0 kPa 条件下， 反应 0.5h， 生成 (S)-methyl 3-dimethoxyphosphorylbutyrate
  参考文献：
  名称：

  Synthesis of New 3-(Dialkoxyphosphoryl)butenoates and Their Enantioselective Hydrogenation

  摘要：

  DOI：

  10.1055/s-1999-3508
• 作为产物：
  描述：

  Methyl 3-(dimethoxyphosphoryl)but-2-enoate 在 palladium diacetate 作用下， 以 Petroleum ether 为溶剂， 反应 48.0h， 以78%的产率得到Methyl 3-(dimethoxyphosphoryl)but-3-enoate
  参考文献：
  名称：

  Synthesis of New 3-(Dialkoxyphosphoryl)butenoates and Their Enantioselective Hydrogenation

  摘要：

  DOI：

  10.1055/s-1999-3508

文献信息

• Cooperative attractive interactions in asymmetric hydrogenations with dihydroxydiphosphine Rh(I) catalysts — a competition study
  作者：Jens Holz、Renat Kadyrov*、Susanne Borns、Detlef Heller、Armin Börner*

  DOI：10.1016/s0022-328x(00)00071-1

  日期：2000.5

  Studies for controlling rate and enantioselectivity of the asymmetric hydrogenation with Rh-diphosphine catalysts by cooperative attractive interactions within the framework of catalyst-substrate complexes are represented. In strong contrast to a Rh(I)[three-1,4-bis(diphenylphosphino)butane-2,3-diol] catalyst an extremely fast reaction took place applying the complex of the analogue erythro ligand. This is likely due to a strong intramolecular hydrogen bond between the vicinal HO groups impeding the hemilabile coordination of one of the hydroxy groups on the metal center during the hydrogenation. When a substrate with strong hydrogen bond acceptor properties such as (E)-methyl 3-dimethoxyphosphorylbut-2-enoate was hydrogenated even the three catalyst exhibited a fast reaction. The product was obtained in 83% ee. In contrast, when in the ligand both HO groups were replaced by MeO groups only poor conversion and 24% ee were achieved. While with the complex bearing HO groups in methanolic solution the corresponding diastereomeric catalyst substrate complexes were dominant, analogue MeO groups bearing catalyst substrate complexes could not be detected by NMR. For the latter, only the Rh(I)-solvent complex was found revealing the high importance of the additional functional groups on this equilibrium. (C) 2000 Elsevier Science S.A. All rights reserved.
• Synthesis of New 3-(Dialkoxyphosphoryl)butenoates and Their Enantioselective Hydrogenation
  作者：Renat Kadyrov

  DOI：10.1055/s-1999-3508

  日期：1999.6