3,5,6-trideoxy-3,5-bis(diphenylphosphine)-1,2-O-isopropylidene-α-D-glucofuranose | 330814-15-8

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 3,5,6-trideoxy-3,5-bis(diphenylphosphine)-1,2-O-isopropylidene-α-D-glucofuranose
• 英文别名: 3,5,6-trideoxy-3,5-bis-diphenylphosphine-1,2-O-isopropylidene-α-L-glucofuranose；[(1R)-1-[(3aR,5R,6R,6aS)-6-diphenylphosphanyl-2,2-dimethyl-3a,5,6,6a-tetrahydrofuro[2,3-d][1,3]dioxol-5-yl]ethyl]-diphenylphosphane
• CAS: 330814-15-8
• 化学式: C₃₃H₃₄O₃P₂
• 分子量: 540.579
• InChiKey: WKCVGTYNMPPOAI-JVQWKRKKSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.5
• 重原子数：
  38
• 可旋转键数：
  7
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.27
• 拓扑面积：
  27.7
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  bis(1,5-cyclooctadiene)rhodium(I) tetrafluoroborate 、 3,5,6-trideoxy-3,5-bis(diphenylphosphine)-1,2-O-isopropylidene-α-D-glucofuranose 以 二氯甲烷 为溶剂， 生成 [Rh(1,5-cyclooctadiene)(3,5,6-trideoxy-3,5-bis-diphenylphosphine-1,2-O-isopropylidene-α-L-glucofuranose)]BF4
  参考文献：
  名称：

  Synthesis and structural studies of rhodium(I)-catalytic precursors containing two furanoside diphosphines

  摘要：

  We have prepared new rhodium(I) complexes with two furanoside diphosphines, 3,5,6-trideoxy-3,5-bis-diphenylphosphine-1, 2-O-isopropylidene-beta -L-idofuranose (1) and 3,5,6-trideoxy-3,5-bis-diphenylphosphine-1,2-O-isopropylidene-alpha -L-glucofuranose (2), which form six-membered chelate rings when they coordinate to rhodium. NMR spectroscopy of the Rh complexes and molecular mechanics calculations showed that the configuration of the stereocenter C-5 greatly influences the structure of these complexes, and thus their enantioselectivity. The pre-catalyst [Rh(cod)(2)]BF4, which gives the highest enantioselectivities in the asymmetric hydrogenation of alkenes, adopts the twist-lambda conformation. By changing the configuration of the C-5, the complex becomes fluxional at room temperature and enantioselectivity drops considerably. (C) 2001 Elsevier Science B.V. All rights reserved.

  DOI：

  10.1016/s0022-328x(01)00819-1
• 作为产物：
  描述：

  1,2-O-isopropylidene-6-deoxy-β-L-talofuranose 在 吡啶 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 0.83h， 生成 3,5,6-trideoxy-3,5-bis(diphenylphosphine)-1,2-O-isopropylidene-α-D-glucofuranose
  参考文献：
  名称：

  Synthesis of novel diphosphines from d-(+)-glucose. Use in asymmetric hydrogenation

  摘要：

  A new family of bidentate diphosphine ligands which contain a glucofuranoside as a simple but highly effective chiral backbone are reported. These ligands are prepared in a few steps from readily available D-(+)-glucose. These new ligands have been applied to the rhodium-catalysed hydrogenation of cl,p-unsaturated carboxylic acid derivatives under very mild reaction conditions, with enantiomeric excesses of up to 98%. (C) 2001 Elsevier Science Ltd. An rights reserved.

  DOI：

  10.1016/s0957-4166(00)00440-7

文献信息

• Synthesis of novel diphosphines from d-(+)-glucose. Use in asymmetric hydrogenation
  作者：Montserrat Diéguez、Oscar Pàmies、Aurora Ruiz、Sergio Castillón、Carmen Claver

  DOI：10.1016/s0957-4166(00)00440-7

  日期：2000.12

  A new family of bidentate diphosphine ligands which contain a glucofuranoside as a simple but highly effective chiral backbone are reported. These ligands are prepared in a few steps from readily available D-(+)-glucose. These new ligands have been applied to the rhodium-catalysed hydrogenation of cl,p-unsaturated carboxylic acid derivatives under very mild reaction conditions, with enantiomeric excesses of up to 98%. (C) 2001 Elsevier Science Ltd. An rights reserved.
• Synthesis and structural studies of rhodium(I)-catalytic precursors containing two furanoside diphosphines
  作者：Montserrat Diéguez、Oscar Pàmies、Aurora Ruiz、Carmen Claver

  DOI：10.1016/s0022-328x(01)00819-1

  日期：2001.6

  We have prepared new rhodium(I) complexes with two furanoside diphosphines, 3,5,6-trideoxy-3,5-bis-diphenylphosphine-1, 2-O-isopropylidene-beta -L-idofuranose (1) and 3,5,6-trideoxy-3,5-bis-diphenylphosphine-1,2-O-isopropylidene-alpha -L-glucofuranose (2), which form six-membered chelate rings when they coordinate to rhodium. NMR spectroscopy of the Rh complexes and molecular mechanics calculations showed that the configuration of the stereocenter C-5 greatly influences the structure of these complexes, and thus their enantioselectivity. The pre-catalyst [Rh(cod)(2)]BF4, which gives the highest enantioselectivities in the asymmetric hydrogenation of alkenes, adopts the twist-lambda conformation. By changing the configuration of the C-5, the complex becomes fluxional at room temperature and enantioselectivity drops considerably. (C) 2001 Elsevier Science B.V. All rights reserved.