(R)-1-phenyl-2,5-pentane-bis-mesylate | 437606-65-0

• 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: (R)-1-phenyl-2,5-pentane-bis-mesylate
• 英文别名: (R)-1-phenyl-2,5-pentanedimesylate；[(4R)-4-methylsulfonyloxy-5-phenylpentyl] methanesulfonate
• CAS: 437606-65-0
• 化学式: C₁₃H₂₀O₆S₂
• 分子量: 336.43
• InChiKey: LTTVKZJNGQATES-CYBMUJFWSA-N

物化性质

• 沸点：
  558.7±50.0 °C(Predicted)
• 密度：
  1.294±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.8
• 重原子数：
  21
• 可旋转键数：
  9
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.54
• 拓扑面积：
  104
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  (R)-1-phenyl-2,5-pentane-bis-mesylate 在 tetrafluoroboric acid 、 正丁基锂 、 仲丁基锂 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 3.0h， 生成 1,2-bis((1R,2R)-2-benzylphospholano)ethane
  参考文献：
  名称：

  Synthesis of Both Enantiomers of a P-Chirogenic 1,2-Bisphospholanoethane Ligand via Convergent Routes and Application to Rhodium-Catalyzed Asymmetric Hydrogenation of CI-1008 (Pregabalin)

  摘要：

  Both enantiomers of a P-chirogenic 1,2-bisphospholanoethane ligand are synthesized via two convergent methods. The first method relies on the chiral alkylation of 1 -((-)-menthoxy)phospholaneborane using a s-BuLi/(-)-sparteine derived chiral base. Only one enantiomer of the catalyst could be synthesized via this method because only one antipode of sparteine is available in nature. The second route relies on the combination of methylphosphine borane and a chiral 1,4-diol. Either enantiomer of the ligand can be synthesized via the second route from the appropriate enantiomer of the 1,4-diol. Asymmetric hydrogenation using catalyst precursor 36 on acetamidoacrylic acid derivatives provided modest to good enantioselectivity (77-95% ee) under low H-2 pressure (30 psi). Asymmetric hydrogenation of Cl-1008 (pregabalin) precursors, 39 and 40, provided good enantioselectivities (92%) at high catalyst loading (1 mol %) and low pressure (30 psi). Enantiomeric excesses dropped sharply with catalyst loading at this pressure. Increasing the pressure of H-2 caused a significant increase in enantiomeric excess for low catalyst loading reactions. Several studies were undertaken to further investigate the enantioselectivity dependence on both pressure and catalyst loading.

  DOI：

  10.1021/ja034715o
• 作为产物：
  描述：

  (S)-(2,3-epoxypropyl)benzene 在 lithium aluminium tetrahydride 、 乙醇 、 sodium 、 三乙胺 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 20.58h， 生成 (R)-1-phenyl-2,5-pentane-bis-mesylate
  参考文献：
  名称：

  Synthesis of Both Enantiomers of a P-Chirogenic 1,2-Bisphospholanoethane Ligand via Convergent Routes and Application to Rhodium-Catalyzed Asymmetric Hydrogenation of CI-1008 (Pregabalin)

  摘要：

  Both enantiomers of a P-chirogenic 1,2-bisphospholanoethane ligand are synthesized via two convergent methods. The first method relies on the chiral alkylation of 1 -((-)-menthoxy)phospholaneborane using a s-BuLi/(-)-sparteine derived chiral base. Only one enantiomer of the catalyst could be synthesized via this method because only one antipode of sparteine is available in nature. The second route relies on the combination of methylphosphine borane and a chiral 1,4-diol. Either enantiomer of the ligand can be synthesized via the second route from the appropriate enantiomer of the 1,4-diol. Asymmetric hydrogenation using catalyst precursor 36 on acetamidoacrylic acid derivatives provided modest to good enantioselectivity (77-95% ee) under low H-2 pressure (30 psi). Asymmetric hydrogenation of Cl-1008 (pregabalin) precursors, 39 and 40, provided good enantioselectivities (92%) at high catalyst loading (1 mol %) and low pressure (30 psi). Enantiomeric excesses dropped sharply with catalyst loading at this pressure. Increasing the pressure of H-2 caused a significant increase in enantiomeric excess for low catalyst loading reactions. Several studies were undertaken to further investigate the enantioselectivity dependence on both pressure and catalyst loading.

  DOI：

  10.1021/ja034715o

文献信息

• US7230135B2
  申请人：——

  公开号：US7230135B2

  公开（公告）日：2007-06-12
• Synthesis of Both Enantiomers of a P-Chirogenic 1,2-Bisphospholanoethane Ligand via Convergent Routes and Application to Rhodium-Catalyzed Asymmetric Hydrogenation of CI-1008 (Pregabalin)
  作者：Garrett Hoge

  DOI：10.1021/ja034715o

  日期：2003.8.1

  Both enantiomers of a P-chirogenic 1,2-bisphospholanoethane ligand are synthesized via two convergent methods. The first method relies on the chiral alkylation of 1 -((-)-menthoxy)phospholaneborane using a s-BuLi/(-)-sparteine derived chiral base. Only one enantiomer of the catalyst could be synthesized via this method because only one antipode of sparteine is available in nature. The second route relies on the combination of methylphosphine borane and a chiral 1,4-diol. Either enantiomer of the ligand can be synthesized via the second route from the appropriate enantiomer of the 1,4-diol. Asymmetric hydrogenation using catalyst precursor 36 on acetamidoacrylic acid derivatives provided modest to good enantioselectivity (77-95% ee) under low H-2 pressure (30 psi). Asymmetric hydrogenation of Cl-1008 (pregabalin) precursors, 39 and 40, provided good enantioselectivities (92%) at high catalyst loading (1 mol %) and low pressure (30 psi). Enantiomeric excesses dropped sharply with catalyst loading at this pressure. Increasing the pressure of H-2 caused a significant increase in enantiomeric excess for low catalyst loading reactions. Several studies were undertaken to further investigate the enantioselectivity dependence on both pressure and catalyst loading.