(+/-)-2,2'-bis(diphenylphosphino)-1,1'-bibenzimidazole | 175871-69-9

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 苯并咪唑类
• 英文名称: (+/-)-2,2'-bis(diphenylphosphino)-1,1'-bibenzimidazole
• 英文别名: [1-(2-Diphenylphosphanylbenzimidazol-1-yl)benzimidazol-2-yl]-diphenylphosphane
• CAS: 175871-69-9
• 化学式: C₃₈H₂₈N₄P₂
• 分子量: 602.615
• InChiKey: OPWYAUGTRDDDOH-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  9.1
• 重原子数：
  44
• 可旋转键数：
  7
• 环数：
  8.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  35.6
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (+/-)-2,2'-bis(diphenylphosphino)-1,1'-bibenzimidazole 在 双氧水 作用下， 以 水 为溶剂， 反应 1.0h， 以90%的产率得到2,2'-bis(diphenylphosphinyl)-1,1'-bibenzimidazole
  参考文献：
  名称：

  Chiral atropisomeric five-membered biheteroaromatic diphosphines: New ligands of the bibenzimidazole and biindole series

  摘要：

  Two new chiral atropisomeric biheteroaromatic diphosphines are described: 2,2'-bis(diphenylphosphino)-1,1'-bibenzimidazole (3a) and 3,3'-dimethyl-1,1'-bis(diphenylphosphino)-2,2'-biindole (4a) structural characterization is given and configurational stability at room temperature demonstrated. The oxidation potential was recognized as a good tool to evaluate the electronic availability of the phosphorus atom in the series of biheteroaromatic diphosphines. Its value increases parallel to the electronic demand of the heterocyclic system and also depends on the position of the diphenylphosphino group. (C) 1997 Elsevier Science S.A.

  DOI：

  10.1016/s0022-328x(96)06682-x
• 作为产物：
  描述：

  2,2'-dimethyl-1,1'-bibenzimidazole 在 potassium permanganate 、 正丁基锂 、 selenium(IV) oxide 、 四甲基乙二胺 、 sodium carbonate 作用下， 以 四氢呋喃 、 1,4-二氧六环 、 正己烷 、 水 、 苯 为溶剂， 反应 17.0h， 生成 (+/-)-2,2'-bis(diphenylphosphino)-1,1'-bibenzimidazole
  参考文献：
  名称：

  Chiral atropisomeric five-membered biheteroaromatic diphosphines: New ligands of the bibenzimidazole and biindole series

  摘要：

  Two new chiral atropisomeric biheteroaromatic diphosphines are described: 2,2'-bis(diphenylphosphino)-1,1'-bibenzimidazole (3a) and 3,3'-dimethyl-1,1'-bis(diphenylphosphino)-2,2'-biindole (4a) structural characterization is given and configurational stability at room temperature demonstrated. The oxidation potential was recognized as a good tool to evaluate the electronic availability of the phosphorus atom in the series of biheteroaromatic diphosphines. Its value increases parallel to the electronic demand of the heterocyclic system and also depends on the position of the diphenylphosphino group. (C) 1997 Elsevier Science S.A.

  DOI：

  10.1016/s0022-328x(96)06682-x

文献信息

• PROCESS FOR PRODUCING OPTICALLY ACTIVE AMINE
  申请人：TAKASAGO INTERNATIONAL CORPORATION

  公开号：US20150210657A1

  公开（公告）日：2015-07-30

  A process for producing an optically active amine compound, characterized by asymmetrically hydrogenating a prochiral carbon-nitrogen double bond in the presence of a ruthenium complex represented by general formula (1) or (2) (wherein P represents an optically active diphosphine, X represents an anionic group, and Ar represents an optionally substituted arylene group).

  一种制备光学活性胺化合物的方法，其特征在于在存在由通用式（1）或（2）表示的钌配合物的情况下，对一个丙半胱氨基双键进行不对称氢化（其中P代表光学活性二膦，X代表阴离子基团，Ar代表可选择取代的芳基基团）。
• “In situ” Activation of Racemic Ru ^II Complexes: Separation of <i>trans</i> and <i>cis</i> Species and Their Application in Asymmetric Reduction
  作者：Giorgio Facchetti、Edoardo Cesarotti、Michela Pellizzoni、Daniele Zerla、Isabella Rimoldi

  DOI：10.1002/ejic.201200643

  日期：2012.9

  Ruthenium(II) dichlorides with racemic atropos-biaryl-based diphosphanes and optically active 1,2-diphenylethane-1,2-diamine (DPEN) as ligands have been synthesised. trans and cis isomers were formed due to the low basicity of the diphosphane ligands, in particular, with BITIANP and BIMIP. The trans and cis species were easily separated by filtration. In particular, when rac-BITIANP was used in combination

  已经合成了具有外消旋 atropos-biaryl-based diphosphanes 和光学活性 1,2-diphenylethane-1,2-diamine (DPEN) 作为配体的二氯化钌 (II)。由于二膦配体的低碱性，特别是 BITIANP 和 BIMIP，形成了反式和顺式异构体。反式和顺式物质很容易通过过滤分离。特别是，当 rac-BITIANP 与手性 DPEN 结合使用时，实现了顺式和反式排列的光学纯配合物的不对称分离，并将它们用作酮不对称氢化中的预催化剂。匹配和错配组合表现出不同的性能。
• Effects of the electronic properties of chiral chelating diphosphines in stereoselective Diels–Alder cycloaddition reactions promoted by their transition metals complexes
  作者：Giuseppe Celentano、Tiziana Benincori、Stefano Radaelli、Mara Sada、Franco Sannicolò

  DOI：10.1016/s0022-328x(01)01459-0

  日期：2002.2

  The Pd(II) and Pt(II) complexes (perchlorates and hexafluoroantimoniates, respectively) of a series of C2 symmetric biheteroaromatic diphosphines differing in their electronic properties at phosphorus have been tested as catalysts in [4+2]-cycloaddition reactions of cyclopentadiene and N-2-alkenoyl-1,3-oxazolidine-2-ones. The best stereoselection results were obtained with the complexes produced from

  在环戊二烯的[4 + 2]-环加成反应中，已测试了一系列在磷上电子性质不同的C 2对称双杂芳族二膦的Pd（II）和Pt（II）配合物（分别为高氯酸盐和六氟锑酸盐）。和N -2-链烯酰基-1，3-恶唑烷-2-酮。由富含电子的配体产生的配合物可获得最佳的立体选择结果，发现该配合物还提供了动力学上最具活性的催化剂。
• Exploiting coordination geometry to selectively predict the σ-donor and π-acceptor abilities of ligands: a back-and-forth journey between electronic properties and spectroscopy
  作者：Marco Fusè、Isabella Rimoldi、Giorgio Facchetti、Sergio Rampino、Vincenzo Barone

  DOI：10.1039/c7cc09627e

  日期：——

  carbonyls of general formula [M(CO)(L′)(L)2] including newly synthesized chlorocarbonyl rhodium complexes with chelating atropoisomeric diphosphanes, we show how coordination geometry can switch the carbonyl stretching frequency into a selective probe of the σ-donor and π-acceptor abilities of the ligands. We thus provide a framework whereby the σ-donation and π-backdonation constituents of the Dewar–Chatt–Duncanson

  通过分析八十个通式[M（CO）（L'）（L）2 ]的四面体和方平面金属羰基化合物，包括新合成的氯羰基铑配合物与螯合的对映异构体二膦，我们展示了配位几何如何改变羰基化合物的拉伸频率进入配体的σ供体和π受体能力的选择性探针。因此，我们提供了一个框架，通过该框架，可以通过有关协同CO部分的光谱数据定量预测杜瓦–查特–邓肯森模型的σ捐赠和π返给成分，反之亦然。
• RUTHENIUM COMPLEX AND METHOD FOR PREPARING OPTICALLY ACTIVE ALCOHOL COMPOUND
  申请人：Nara Hideki

  公开号：US20130041151A1

  公开（公告）日：2013-02-14

  The present invention provides a novel ruthenium complex which has an excellent catalytic activity in terms of reactivity for asymmetric reduction of a carbonyl compound and enantioselectivity, a catalyst using the ruthenium complex, and a method for preparing optically active alcohol compounds using the ruthenium complex. The present invention relates to a ruthenium complex having ruthenacycle structure, a catalyst for asymmetric reduction consisting of the ruthenium complex, and a method for preparing optically active alcohol using the ruthenium complex.

  本发明提供了一种新型的钌配合物，该配合物在对羰基化合物的不对称还原反应中具有优异的催化活性和对映选择性，以及使用该钌配合物的催化剂和制备光学活性醇化合物的方法。本发明涉及一种具有钌环结构的钌配合物，一种由该钌配合物组成的不对称还原催化剂，以及使用该钌配合物制备光学活性醇的方法。