(2R,3S)-1,4-bis(diphenylphosphino)-butan-2,3-diol | 292865-89-5

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: (2R,3S)-1,4-bis(diphenylphosphino)-butan-2,3-diol
• 英文别名: (2R,3S)-1,4-bis(diphenylphosphino)-butane-2,3-diol；(-)-1,4-bis(diphenylphosphino)butane-2,3-diol；(2R,3S)-1,4-bis(diphenylphosphanyl)butane-2,3-diol
• CAS: 292865-89-5
• 化学式: C₂₈H₂₈O₂P₂
• 分子量: 458.477
• InChiKey: AOHZKGPNHXMRGN-HNRBIFIRSA-N

物化性质

• 沸点：
  622.4±55.0 °C(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.6
• 重原子数：
  32
• 可旋转键数：
  9
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.14
• 拓扑面积：
  40.5
• 氢给体数：
  2
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  bis(1,5-cyclooctadiene)rhodium(I) tetrafluoroborate 、 (2R,3S)-1,4-bis(diphenylphosphino)-butan-2,3-diol 以 四氢呋喃 为溶剂， 以63%的产率得到[Rhodium((2R,3S)-1,4-bis(diphenylphosphino)-butane-2,3-diol)(cyclooctadiene)] tetrafluoroborate complex
  参考文献：
  名称：

  Cooperative attractive interactions in asymmetric hydrogenations with dihydroxydiphosphine Rh(I) catalysts — a competition study

  摘要：

  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.

  DOI：

  10.1016/s0022-328x(00)00071-1
• 作为产物：
  描述：

  (2R,3S)-2,3-O-cyclohexylidene-1,4-bis-(diphenylphosphino)-butan-2,3-diol 在 甲烷磺酸 、 水 作用下， 以 甲醇 为溶剂， 以56%的产率得到(2R,3S)-1,4-bis(diphenylphosphino)-butan-2,3-diol
  参考文献：
  名称：

  Cooperative attractive interactions in asymmetric hydrogenations with dihydroxydiphosphine Rh(I) catalysts — a competition study

  摘要：

  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.

  DOI：

  10.1016/s0022-328x(00)00071-1
• 作为试剂：
  描述：

  N-acetamido cinnamic acid 在 bis(1,5-cyclooctadiene)rhodium(I) tetrafluoroborate 氢气 、 (2R,3S)-1,4-bis(diphenylphosphino)-butan-2,3-diol 作用下， 以 甲醇 为溶剂， 25.0 ℃ 、100.0 kPa 条件下， 生成 N-乙酰-DL-苯丙氨酸
  参考文献：
  名称：

  Cooperative attractive interactions in asymmetric hydrogenations with dihydroxydiphosphine Rh(I) catalysts — a competition study

  摘要：

  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.

  DOI：

  10.1016/s0022-328x(00)00071-1

文献信息

• Immobilization of chiral cationic diphosphine rhodium complexes in nanopores of mesoporous silica and application in asymmetric hydrogenation
  作者：Reine Sayah、Marie Le Floch、Eric Framery、Véronique Dufaud

  DOI：10.1016/j.molcata.2009.08.025

  日期：2010.1.2

  ate under various reaction conditions (pressure and temperature). Generally, the activity of supported catalysts was high as full conversions were obtained but immobilization of the system leads to significant loss of enantioselectivity. The best ee (20%) was observed in the case of the catalyst whose surface had been passivated prior to the grafting but the enantiomeric excesses were fairly below

  通过共价固定在SBA型二氧化硅上，制备了具有衍生自（-）-2,2-二甲基-4,5-双（二苯基膦基）甲基）-1,3-二氧戊环（DIOP）的二齿膦的异质手性阳离子铑配合物。为了将系链引入表面，必须通过由水解和与有机硅氧烷前体的缩合组成的反应顺序来化学修饰DIOP配体。在经典的接枝程序下，制备了两种基于SBA-15的阳离子铑杂化材料和部分封端的SBA-3型二氧化硅。使用多种分子和固态技术对催化固体进行了全面表征，以确定它们的结构和质地特性。然后在甲基（Z）-2- N-乙酰氨基肉桂酸酯在各种反应条件（压力和温度）下。通常，当获得完全转化时，负载型催化剂的活性较高，但是体系的固定化导致对映选择性的显着损失。对于在接枝之前表面已被钝化的催化剂，观察到最佳ee（20％），但对映体过量值明显低于均相催化值。
• KNIERZINGER, ANDREAS;WALTHER, WILLY;WEBER, BEAT;MULLER, ROBERT KARL;NETSC+, HELV. CHIM. ACTA, 73,(1990) N, C. 1087-1107
  作者：KNIERZINGER, ANDREAS、WALTHER, WILLY、WEBER, BEAT、MULLER, ROBERT KARL、NETSC+

  DOI：——

  日期：——