1,2-bis(2,5-diphenylphospholano)methane | 933474-81-8

• 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: 1,2-bis(2,5-diphenylphospholano)methane
• 英文别名: (R,R)-Ph-BPM；1,2-bis[(R,R)-2,5-diphenylphospholano]methane；(2R,5R)-1-[[(2R,5R)-2,5-diphenylphospholan-1-yl]methyl]-2,5-diphenylphospholane
• CAS: 933474-81-8
• 化学式: C₃₃H₃₄P₂
• 分子量: 492.58
• InChiKey: UETSYBQYFQMSPB-XEXPGFJZSA-N

物化性质

• 沸点：
  638.6±55.0 °C(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  6.8
• 重原子数：
  35
• 可旋转键数：
  6
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.27
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为反应物：
  描述：

  1,2-bis(2,5-diphenylphospholano)methane 、 [ruthenium(II)(η⁶-1-methyl-4-isopropyl-benzene)(chloride)(μ-chloride)]₂ 以 乙醇 、 二氯甲烷 为溶剂， 反应 2.0h， 以100%的产率得到chloro-{1,2-bis[(R,R)-2,5-diphenylphospholano]methane}(p-cymene)ruthenium(II) chloride
  参考文献：
  名称：

  WO2007/123957

  摘要：

  公开号：
• 作为产物：
  描述：

  在 三乙烯二胺 、 正丁基锂 、 四甲基乙二胺 作用下， 以 四氢呋喃 为溶剂， 生成 1,2-bis(2,5-diphenylphospholano)methane
  参考文献：
  名称：

  1,2-Bis(2,5-diphenylphospholano)methane, a new ligand for asymmetric hydrogenation

  摘要：

  1,2-Bis(2,5-diphenylphospholano)methane (Ph-BPM) has been prepared in good yield from 2,5-trans-diphenylphospholane-borane adduct. Rhodium and ruthenium complexes of this ligand have been prepared and their usefulness in asymmetric hydrogenation has been investigated. [Ph-BPM Rh(COD)]BF4 showed high activity and selectivity for itaconate and dehydroamino acid hydrogenation. Ph-BPM RUCl2(DPEN) was effective for imine hydrogenation. (c) 2007 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetlet.2007.01.018
• 作为试剂：
  描述：

  烯丙基腈 在 1,2-bis(2,5-diphenylphospholano)methane 、 acetylacetonatodicarbonylrhodium(l) 一氧化碳 、 氢气 作用下， 以 甲苯 为溶剂， 80.0 ℃ 、1.03 MPa 条件下， 反应 3.0h， 以2%的产率得到
  参考文献：
  名称：

  WO2007/123957

  摘要：

  公开号：

文献信息

• BISPHOSPHOLANES FOR USE AS CATALYSTS IN ASYMMETRIC REACTIONS
  申请人：Jackson Philip M.

  公开号：US20090099358A1

  公开（公告）日：2009-04-16

  The invention is a set of novel bisphospholane ligands that can be complexed with transition metals. These complexes are useful as catalysts in asymmetric reactions such as asymmetric hydrogenation.

  这项发明是一组新型的双膦醇配体，可以与过渡金属形成配合物。这些配合物可用作不对称反应催化剂，例如不对称氢化反应。
• Bridging Group Effects in Chelating Bis(2,5-diphenylphospholane) Ligands for Rhodium-Catalyzed Asymmetric Hydroformylation
  作者：Alex T. Axtell、Jerzy Klosin、Gregory T. Whiteker、Christopher J. Cobley、Martin E. Fox、Mark Jackson、Khalil A. Abboud

  DOI：10.1021/om9000583

  日期：2009.5.25

  A series of seven bis(2,5-diphenylphospholane) ligands has been evaluated for utility in rhodium-catalyzed asymmetric hydroformylation. The ligands differ in the nature of the moiety that bridges the two phospholane rings. Hydroformylation of styrene, vinyl acetate, and allyl cyanide was performed in tandem using parallel pressure vessels. Significant differences in rate, regioselectivity, and enantioselectivity were observed between catalysts. Ligands with two-carbon bridges exhibited selectivities comparable to the ethylene-bridged (S,S)-Ph-BPE. Electron-deficient heterocyclic bridges (pyrazine and quinoxaline) gave increased rates over (S,S)-Ph-BPE. Bis(2,5-diphenylphospholane) ligands with -CH2-, -CH2CH2CH2-, and 1,1'-ferrocenyl bridges led to significantly lower selectivities and rates than (S,S)-Ph-BPE. X-ray crystal structures of [(SS`)-Ph-Quinoxaline]Rh(acac), [(R,R)-Ph-BPM]Rh(acac), and [(SS)-Ph-5-Fc]Rh(acac) are reported. The P-Rh-P bite angles in these complexes are 87.46(3)degrees, 74.10(5)degrees, and 99.06(3)degrees, respectively. As with asymmetric olefin hydrogenation using bis-phospholane ligands, the maximum enantioselectivity in asymmetric hydroformylation was found with bis-phospholanes that adopt P-Rh-P bite angles near 85 degrees.
• US7935841B2
  申请人：——

  公开号：US7935841B2

  公开（公告）日：2011-05-03
• WO2007/123957
  申请人：——

  公开号：——

  公开（公告）日：——
• 1,2-Bis(2,5-diphenylphospholano)methane, a new ligand for asymmetric hydrogenation
  作者：Mark Jackson、Ian C. Lennon

  DOI：10.1016/j.tetlet.2007.01.018

  日期：2007.3

  1,2-Bis(2,5-diphenylphospholano)methane (Ph-BPM) has been prepared in good yield from 2,5-trans-diphenylphospholane-borane adduct. Rhodium and ruthenium complexes of this ligand have been prepared and their usefulness in asymmetric hydrogenation has been investigated. [Ph-BPM Rh(COD)]BF4 showed high activity and selectivity for itaconate and dehydroamino acid hydrogenation. Ph-BPM RUCl2(DPEN) was effective for imine hydrogenation. (c) 2007 Elsevier Ltd. All rights reserved.