(R)-(6,6'-difluorobiphenyl-2,2'-diyl)bis(diphenylphosphine) | 159345-95-6

• 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)-(6,6'-difluorobiphenyl-2,2'-diyl)bis(diphenylphosphine)
• 英文别名: (RS)-(6,6'-difluorobiphenyl-2,2'-diyl)bis(diphenylphosphine)；(S)-(6,6'-difluorobiphenyl-2,2'-diyl)bis(diphenylphosphine)；[2-(2-Diphenylphosphanyl-6-fluorophenyl)-3-fluorophenyl]-diphenylphosphane
• CAS: 159345-95-6
• 化学式: C₃₆H₂₆F₂P₂
• 分子量: 558.547
• InChiKey: RAQOYWRBQFMPCA-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  9.1
• 重原子数：
  40
• 可旋转键数：
  7
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (R)-(6,6'-difluorobiphenyl-2,2'-diyl)bis(diphenylphosphine) 在 双氧水 作用下， 以 甲醇 、 甲苯 为溶剂， 以94%的产率得到(RS)-(6,6'-difluorobiphenyl-2,2'-diyl)bis(diphenylphosphine oxide)
  参考文献：
  名称：

  Efficient synthesis of (R)- and (S)-(6,6′-difluorobiphenyl-2,2′-diyl) bis(diphenylphosphine); electron-poor biphenyl-type ligands for transition metal catalysts.

  摘要：

  Racemic title compound (RS)-5 is synthesized (Scheme 1, 100g scale) in four simple steps (49% overall yield) from meta-fluorobromobenzene 1. (RS)-5 is efficiently resolved (Scheme 2) utilizing commercial (S)-(+)-dipalladium complex 9 to give homochiral (S)-(+)-5 and (R)-(-)-5 in 75 and 95% of theoretical yield, respectively. Enantiomerically pure diphosphines (S)-5 and (R)-5 do not racemize in organic solutions, even when heated to 207 degrees C. Homochiral palladium(ll) dichloride complexes (-)-11 and (+)-11 are prepared in quantitative yield. Insitu rhodium(I)-complex of homochiral 5 is ail efficient catalyst for alkene hydroboration by catecholborane and requires high hydrogen pressure to catalyze hydrogenation.Interesting anomalies of the specific rotation are observed for homochiral diphosphines (S)-(+)5 and (R)-(-)-5. The specific rotation [alpha](25)(D) of (S)-(+)-5 measured in similar aromatic hydrocarbons (toluene, o-xylene, mesitylene, tetralin) varies from +114.9 (c 0.99, toluene) to 73.9(c 0.46, tetralin).

  DOI：

  10.1016/0957-4166(94)80172-x
• 作为产物：
  描述：

  (RS)-(6,6'-difluorobiphenyl-2,2'-diyl)bis(diphenylphosphine oxide) 在 三正丁胺 、 dichloromethylsilane 作用下， 以 xylene 为溶剂， 反应 86.0h， 以92%的产率得到(R)-(6,6'-difluorobiphenyl-2,2'-diyl)bis(diphenylphosphine)
  参考文献：
  名称：

  Efficient synthesis of (R)- and (S)-(6,6′-difluorobiphenyl-2,2′-diyl) bis(diphenylphosphine); electron-poor biphenyl-type ligands for transition metal catalysts.

  摘要：

  Racemic title compound (RS)-5 is synthesized (Scheme 1, 100g scale) in four simple steps (49% overall yield) from meta-fluorobromobenzene 1. (RS)-5 is efficiently resolved (Scheme 2) utilizing commercial (S)-(+)-dipalladium complex 9 to give homochiral (S)-(+)-5 and (R)-(-)-5 in 75 and 95% of theoretical yield, respectively. Enantiomerically pure diphosphines (S)-5 and (R)-5 do not racemize in organic solutions, even when heated to 207 degrees C. Homochiral palladium(ll) dichloride complexes (-)-11 and (+)-11 are prepared in quantitative yield. Insitu rhodium(I)-complex of homochiral 5 is ail efficient catalyst for alkene hydroboration by catecholborane and requires high hydrogen pressure to catalyze hydrogenation.Interesting anomalies of the specific rotation are observed for homochiral diphosphines (S)-(+)5 and (R)-(-)-5. The specific rotation [alpha](25)(D) of (S)-(+)-5 measured in similar aromatic hydrocarbons (toluene, o-xylene, mesitylene, tetralin) varies from +114.9 (c 0.99, toluene) to 73.9(c 0.46, tetralin).

  DOI：

  10.1016/0957-4166(94)80172-x

文献信息

• CHIRAL LIGAND-BASED METAL-ORGANIC FRAMEWORKS FOR BROAD-SCOPE ASYMMETRIC CATALYSIS
  申请人：The University of Chicago

  公开号：US20170173572A1

  公开（公告）日：2017-06-22

  Metal-organic framework (MOFs) compositions based on chiral phosphine-, chiral oxazoline-, chiral pyridine-, and chiral diene-derived organic bridging ligands were synthesized and then post-synthetically metalated with metal precursors such as Ru and Rh complexes. The metal complexes could also be directly incorporated into the MOFs. The MOFs provide a versatile family of recyclable and reusable single-site solid catalysts for catalyzing a variety of asymmetric organic transformations, including the addition of arylboronic acids to α,β-unsaturated ketones and alkimines, the hydrogenation of substituted alkene and carbonyl compounds, and cyclization reactions. The solid catalysts can also be integrated into a flow reactor or a supercritical fluid reactor.
• Efficient synthesis of (R)- and (S)-(6,6′-difluorobiphenyl-2,2′-diyl) bis(diphenylphosphine); electron-poor biphenyl-type ligands for transition metal catalysts.
  作者：Heiner Jendralla、Chang Hua Li、Erich Paulus

  DOI：10.1016/0957-4166(94)80172-x

  日期：1994.7

  Racemic title compound (RS)-5 is synthesized (Scheme 1, 100g scale) in four simple steps (49% overall yield) from meta-fluorobromobenzene 1. (RS)-5 is efficiently resolved (Scheme 2) utilizing commercial (S)-(+)-dipalladium complex 9 to give homochiral (S)-(+)-5 and (R)-(-)-5 in 75 and 95% of theoretical yield, respectively. Enantiomerically pure diphosphines (S)-5 and (R)-5 do not racemize in organic solutions, even when heated to 207 degrees C. Homochiral palladium(ll) dichloride complexes (-)-11 and (+)-11 are prepared in quantitative yield. Insitu rhodium(I)-complex of homochiral 5 is ail efficient catalyst for alkene hydroboration by catecholborane and requires high hydrogen pressure to catalyze hydrogenation.Interesting anomalies of the specific rotation are observed for homochiral diphosphines (S)-(+)5 and (R)-(-)-5. The specific rotation [alpha](25)(D) of (S)-(+)-5 measured in similar aromatic hydrocarbons (toluene, o-xylene, mesitylene, tetralin) varies from +114.9 (c 0.99, toluene) to 73.9(c 0.46, tetralin).