2,2'-bis(diphenylphosphinoamino)-5,5'-(octamethylenedioxy)-1,1'-biphenyl | 1026067-55-9

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 2,2'-bis(diphenylphosphinoamino)-5,5'-(octamethylenedioxy)-1,1'-biphenyl
• 英文别名: 2,2'-bis(diphenylphosphinoamino)-5,5'-(octamethylenedioxy)-1,10-biphenyl；3-N,20-N-bis(diphenylphosphanyl)-7,16-dioxatricyclo[15.3.1.12,6]docosa-1(20),2,4,6(22),17(21),18-hexaene-3,20-diamine
• CAS: 1026067-55-9
• 化学式: C₄₄H₄₄N₂O₂P₂
• 分子量: 694.793
• InChiKey: TUPITQKKAUBSCZ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  11.8
• 重原子数：
  50
• 可旋转键数：
  8
• 环数：
  7.0
• sp3杂化的碳原子比例：
  0.18
• 拓扑面积：
  42.5
• 氢给体数：
  2
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  2,2'-bis(diphenylphosphinoamino)-5,5'-(octamethylenedioxy)-1,1'-biphenyl 在 Daicel Chiracel AD-H 作用下， 生成 (R)-(-)-2,2'-bis(diphenylphosphinoamino)-5,5'-(octamethylenedioxy)-1,10-biphenyl 、 (S)-(+)-2,2'-bis(diphenylphosphinoamino)-5,5'-(octamethylenedioxy)-1,10-biphenyl
  参考文献：
  名称：

  Novel atropisomeric aminophosphine ligands with a bridge across the 5,5′-position of biphenyl for Rh(I)-catalyzed asymmetric hydrogenation

  摘要：

  A new type of atropisomeric bisaminophosphine ligands 2 with a bridge across the 5,5'-position of biphenyl has been developed. The axial chirality of this type of ligands can be retained by macro-ring strain produced from 5,5'-linkage of biphenyl even without 6,6'-substituents on biphenyls. The ligand (R)-2a showed high catalytic activities and enantioselectivities (up to 95.3% ee and quantitative yields) for Rh(I)-catalyzed asymmetric hydrogenation of a variety of methyl (Z)-2-acetamido-3-arylacrylates, (C) 2008 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetlet.2008.04.140
• 作为产物：
  描述：

  2,2'-diamino-5,5'-(octamethylenedioxy)-1,10-biphenyl 、 二苯基氯化膦 在 三乙胺 作用下， 以 二氯甲烷 为溶剂， 反应 24.0h， 以81%的产率得到2,2'-bis(diphenylphosphinoamino)-5,5'-(octamethylenedioxy)-1,1'-biphenyl
  参考文献：
  名称：

  Synthesis of atropisomeric 5,5′-linked biphenyl bisaminophosphine ligands and their applications in asymmetric catalysis

  摘要：

  Atropisomeric 5,5'-linked biphenyl bisaminophosphine ligands 2 has been synthesized. The axial chirality of this type of ligands can be retained by macro ring strain produced from 5,5'-linkage of biphenyl even without 6,6'-substituents on biphenyls. The Rh complex of bisaminophosphine 2a as a catalyst is effectively working in the asymmetric hydrogenation of methyl (Z)-2-acetamido-3-arylacrylates, however, for hydrogenation of arylenamide, the low enantioselectivity was observed. When the ligands applied to Pd-catalyzed allylic alkylation, it is found that ligand 2b having a longer backbone linkage is a better ligand for enantioselection in the reaction. (C) 2008 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2008.12.056

文献信息

• Novel atropisomeric aminophosphine ligands with a bridge across the 5,5′-position of biphenyl for Rh(I)-catalyzed asymmetric hydrogenation
  作者：Hao Wei、Yong Jian Zhang、Yijun Dai、Jiaming Zhang、Wanbin Zhang

  DOI：10.1016/j.tetlet.2008.04.140

  日期：2008.6

  A new type of atropisomeric bisaminophosphine ligands 2 with a bridge across the 5,5'-position of biphenyl has been developed. The axial chirality of this type of ligands can be retained by macro-ring strain produced from 5,5'-linkage of biphenyl even without 6,6'-substituents on biphenyls. The ligand (R)-2a showed high catalytic activities and enantioselectivities (up to 95.3% ee and quantitative yields) for Rh(I)-catalyzed asymmetric hydrogenation of a variety of methyl (Z)-2-acetamido-3-arylacrylates, (C) 2008 Elsevier Ltd. All rights reserved.
• Synthesis of atropisomeric 5,5′-linked biphenyl bisaminophosphine ligands and their applications in asymmetric catalysis
  作者：Yong Jian Zhang、Hao Wei、Wanbin Zhang

  DOI：10.1016/j.tet.2008.12.056

  日期：2009.2

  Atropisomeric 5,5'-linked biphenyl bisaminophosphine ligands 2 has been synthesized. The axial chirality of this type of ligands can be retained by macro ring strain produced from 5,5'-linkage of biphenyl even without 6,6'-substituents on biphenyls. The Rh complex of bisaminophosphine 2a as a catalyst is effectively working in the asymmetric hydrogenation of methyl (Z)-2-acetamido-3-arylacrylates, however, for hydrogenation of arylenamide, the low enantioselectivity was observed. When the ligands applied to Pd-catalyzed allylic alkylation, it is found that ligand 2b having a longer backbone linkage is a better ligand for enantioselection in the reaction. (C) 2008 Elsevier Ltd. All rights reserved.