2,2'-bis[di(m-tolyl)phosphino]-1,1'-binaphthyl

• 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: 2,2'-bis[di(m-tolyl)phosphino]-1,1'-binaphthyl
• 英文别名: 2,2'-bis[bis(3-methylphenyl)phosphino]-1,1'-binaphthyl；[1-[2-bis(3-methylphenyl)phosphanylnaphthalen-1-yl]naphthalen-2-yl]-bis(3-methylphenyl)phosphane
• 化学式: C₄₈H₄₀P₂
• 分子量: 678.793
• InChiKey: MJRVUGAHDHEPEL-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  12.9
• 重原子数：
  50
• 可旋转键数：
  7
• 环数：
  8.0
• sp3杂化的碳原子比例：
  0.08
• 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：

  2,2'-bis[di(m-tolyl)phosphino]-1,1'-binaphthyl 、 [RuI₂(p-cymene)] 以 甲醇 、 二氯甲烷 为溶剂， 生成 {RuI((S)-2,2'-bis(bis(3-methylphenyl)phosphino)-1,1'-binaphthyl)(p-cymene)}I
  参考文献：
  名称：

  Highly stereoselective asymmetric hydrogenation of 2-benzamidomethyl-3-oxobutanoate catalysed by cationic binap–ruthenium(II) complexes

  摘要：

  使用[Rul{(R)-binap}(p-cymene)]I 和相应的 binap 衍生物配合物作为催化剂，实现了 2-苯甲酰胺甲基-3-羟基丁酸甲酯的高非对映选择性氢化、得到了(2S,3R)-2-苯甲酰胺基甲基-3-羟基丁酸甲酯，这是一种用于合成δ-内酰胺类抗生素的多功能中间体，非对映异构体过量率高达 98%，对映异构体过量率高达 99%。

  DOI：

  10.1039/c39910000609
• 作为产物：
  描述：

  2,2-二溴-1,1-联萘 在 三氯硅烷 、 碘 、 magnesium 、 三乙胺 作用下， 以 xylene 为溶剂， 反应 3.5h， 生成 2,2'-bis[di(m-tolyl)phosphino]-1,1'-binaphthyl
  参考文献：
  名称：

  Cationic BINAP-Ru(II) Halide Complexes: Highly Efficient Catalysts for Stereoselective Asymmetric Hydrogenation of .alpha.- and .beta.-Functionalized Ketones

  摘要：

  Cationic ruthenium-BINAP complexes 5, 7, and 10 of the formula [RuX((S)-BINAP) (arene)]Y, where X = Cl, Br, I; Y = Cl, Br, I, BF4, B(C6H5)(4); arene = benzene, p-cymene, ethyl benzoate, and their enantiomers have been prepared by the reaction of arene-ruthenium halide complexes 4, 6, and 9 with (S)-BINAP or (R)-BINAP. Structures of the complexes were established by spectroscopy, conductivity, and a single-crystal X-ray analysis (5d: orthorhombic, P2(1)2(1)2; a 20.141(2) Angstrom, b = 18.504(1) Angstrom, c 12.241(1) Angstrom V = 4562.0(7) Angstrom(3), Z = 4, R = 0.078 for unique 4177 reflections). BINAP derivatives with various substituents at the para and meta positions of four phenyl rings on phosphorus atoms and their cationic Ru(II) complexes have also been synthesized. These BINAP-Ru(II) complexes have been used as catalysts for the asymmetric hydrogenation of various unsaturated organic compounds such as alpha- and beta-keto esters, allylic alcohols, and alpha,beta-unsaturated carboxylic acids in excellent diastereo- and/or enantioselectivities. Catalytic activities and stereoselectivities depend highly on reaction conditions such as solvent, temperature, and additives. Variation of halogen ligands bound to ruthenium atom and substituents on four phenyl rings of BINAP also have exerted remarkable effects on the efficiency of the catalysis. Asymmetric hydrogenation of methyl (+/-)-2-(benzamidomethyl)-3-oxobutanoate catalyzed by the species derived from 9c and 3,5((t)Bu)(2)-BINAP afforded the corresponding syn-(2S,3R)-17 in 98% de and 99% ee.

  DOI：

  10.1021/jo00090a026

文献信息

• Axially Asymmetric Phosphorus Compound and Production Method Thereof
  申请人：Tanaka Ken

  公开号：US20090227805A1

  公开（公告）日：2009-09-10

  Problem to be Solved: To provide an axially asymmetric optically active biarylphosphorus compound that can easily produced without the step of optical resolution which was almost indispensable in conventional methods. Solution: A method for producing an axially asymmetric phosphorus compound represented by the general formula (1), comprising a cycloaddition reaction of a compound having a triple bond with the use of a catalyst containing rhodium metal and an optically active bisphosphine. (In the formula, J is an oxygen atom, a sulfur atom or BH 3 ; R 1 and R 2 independently are an alkyl, cycloalkyl, aryl, alkoxy and aryloxy group; a1 and a2 independently are 0 or 1; R 3 to R 10 independently are an alkyl, cycloalkyl, aryl, alkoxy and aryloxy group; two among R 3 to R 10 may form a ring; and * is axial asymmetry.)

  要解决的问题：提供一种轴向不对称的光学活性联苯磷化合物，可以在传统方法中几乎不可或缺的光学分辨步骤之外轻松生产。 解决方案：一种生产由通式（1）表示的轴向不对称磷化合物的方法，包括使用含有铑金属和光学活性双膦的催化剂进行含有三键化合物的环加成反应。 （在公式中，J是氧原子、硫原子或BH3；R1和R2独立地是烷基、环烷基、芳基、烷氧基和芳氧基；a1和a2独立地为0或1；R3到R10独立地是烷基、环烷基、芳基、烷氧基和芳氧基；R3到R10中的两个可能形成环；*表示轴向不对称。）
• PROCESS FOR PRODUCING PHENYL-SUBSTITUTED HETEROCYCLIC DERIVATIVE THROUGH COUPLING USING TRANSITION METAL CATALYST
  申请人：Komiyama Masato

  公开号：US20110313169A1

  公开（公告）日：2011-12-22

  A process for efficiently producing, through few steps either a xanthine oxidase inhibitor, which is a therapeutic agent for hyperuricemia, or an intermediate therefore. The process is a novel coupling process which comprises subjecting a compound represented by formula (1) to coupling reaction with a compound represented by formula (2) in the presence of a transition metal compound to thereby obtain a compound represented by formula (3).

  一种高效生产黄嘌呤氧化酶抑制剂或其中间体的方法，该抑制剂是治疗高尿酸血症的药物。该方法是一种新型偶联过程，包括将式（1）表示的化合物与式（2）表示的化合物在过渡金属化合物存在下进行偶联反应，从而获得式（3）表示的化合物。
• 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）。
• Axially asymmetric ester compound and production method thereof
  申请人：Tanaka Ken

  公开号：US20090299076A1

  公开（公告）日：2009-12-03

  To provide an axially asymmetric optically active biaryl ester compound that can easily produced without the step of optical resolution which was almost indispensable in conventional methods. There is provided a method for producing an axially asymmetric ester compound, comprising a cycloaddition of a compound having a triple bond with the use of a catalyst containing rhodium metal and an optically active bisphosphine.

  提供一种具有轴向不对称光学活性的双芳基酯化合物，可在传统方法中几乎不可或缺的光学分辨步骤之外轻松生产。提供了一种生产轴向不对称酯化合物的方法，包括使用含有铑金属和光学活性双膦催化剂对具有三键的化合物进行环加成。
• IRIDIUM COMPLEXES
  申请人：Mashima Kazushi

  公开号：US20090036696A1

  公开（公告）日：2009-02-05

  The present invention has as its object to provide an iridium complex represented by the general formula: [(l r H L 1 L 2 ) 2 (μ-X 1 )(μ-X 2 )(μ-X 3 )]X 4 (1) (wherein L 1 and L 2 may be the same or different and each represent a monodendate neutral ligand, or each cooperate with the other to form a bidendate neutral ligand; X 1 , X 2 and X 3 may be the same or different, and each represent a halogen atom; and X 4 is a counter-anion). Also, the present invention provides a novel catalyst which can achieve excellent performance as a catalyst for asymmetric synthesis, especially asymmetric hydrogenation, in terms of chemical selectivity, enantioselectivity and catalytic activity, and the like.

  本发明的目的是提供一种铱配合物，其通式表示为：[(l r H L1L2)2(μ-X1)(μ-X2)(μ-X3)]X4(1)（其中L1和L2可以相同也可以不同，每个代表一种单齿中性配体，或者合作形成一种双齿中性配体；X1、X2和X3可以相同也可以不同，每个代表一种卤素原子；X4是一个反离子）。此外，本发明提供了一种新型催化剂，可以在化学选择性、对映选择性和催化活性等方面实现出色的性能，特别是作为不对称合成的催化剂，尤其是不对称氢化反应。