(RS)-6,6'-dibromo-3,3'-dimethoxy-2,2',4,4'-tetramethyl-1,1'-biphenyl | 135630-65-8

• 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: (RS)-6,6'-dibromo-3,3'-dimethoxy-2,2',4,4'-tetramethyl-1,1'-biphenyl
• 英文别名: 1-Bromo-2-(6-bromo-3-methoxy-2,4-dimethylphenyl)-4-methoxy-3,5-dimethylbenzene
• CAS: 135630-65-8
• 化学式: C₁₈H₂₀Br₂O₂
• 分子量: 428.164
• InChiKey: LWTCPXOTEWVULG-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.3
• 重原子数：
  22
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  18.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (RS)-6,6'-dibromo-3,3'-dimethoxy-2,2',4,4'-tetramethyl-1,1'-biphenyl 在 三氯硅烷 、 三乙胺 作用下， 以 氯苯 为溶剂， 生成 (4,4',6,6'-tetramethyl-5,5'-dimethoxybiphenyl-2,2'-diyl)-bis(di-p-methoxyphenylphosphine)
  参考文献：
  名称：

  Synthesis of axially dissymmetric biphenylbisphosphine ligands, bimops and asymmetric hydrogenations of .BETA.-keto ester and .ALPHA.,.BETA.-unsaturated carboxylic acid catalyzed by their ruthenium (II) complexes.

  摘要：

  新设计并合成了轴向非对称的双联苯双膦配体BIMOP（1a）和p-MeO-BIMOP（1b）。通过实验证实，钌(II)配合物(R)-1a和1b在甲基3-氧代丁酸酯和变性腺苷酸不对称氢化中是出色的催化剂，分别得到对映体纯度为95-99%的(R)-甲基3-羟基丁酸酯和86-91%的(R)-2-甲基丁酸。

  DOI：

  10.1248/cpb.39.1085
• 作为产物：
  描述：

  2,6-二甲基硝基苯 在 盐酸 、 溴 、 碘 、 铁粉 、 铜 、 过碘酸 、 亚硝酸异戊酯 作用下， 生成 (RS)-6,6'-dibromo-3,3'-dimethoxy-2,2',4,4'-tetramethyl-1,1'-biphenyl
  参考文献：
  名称：

  Synthesis of axially dissymmetric biphenylbisphosphine ligands, bimops and asymmetric hydrogenations of .BETA.-keto ester and .ALPHA.,.BETA.-unsaturated carboxylic acid catalyzed by their ruthenium (II) complexes.

  摘要：

  新设计并合成了轴向非对称的双联苯双膦配体BIMOP（1a）和p-MeO-BIMOP（1b）。通过实验证实，钌(II)配合物(R)-1a和1b在甲基3-氧代丁酸酯和变性腺苷酸不对称氢化中是出色的催化剂，分别得到对映体纯度为95-99%的(R)-甲基3-羟基丁酸酯和86-91%的(R)-2-甲基丁酸。

  DOI：

  10.1248/cpb.39.1085

文献信息

• Synthesis of an Axially Dissymmetric Biphenylcarboxylate Ligand, BDME, and Asymmetric Cyclopropanation of Olefins with Diazoacetate Catalyzed by Its Dirhodium(II) Complex
  作者：Hitoshi Ishitani、Kazuo Achiwa

  DOI：10.1055/s-1997-5777

  日期：1997.7

  An axially dissymmetric biphenylcarboxylate ligand, BDME (4), has been newly designed and prepared. The dirhodium(II) complex (1) of (4) proved to be an excellent catalyst in asymmetric cyclopropanation of styrene with d-menthyl diazoacetate affording d-menthyl cis-2-phenyl-cyclopropane-1-carboxylate of 99% de.

  一种轴向不对称的二苯甲酸盐配体BDME（4）被新设计和制备。其与(4)的二铑(II)复合物(1)在与d-薄荷基二氮乙酸酯进行不对称环丙烷化反应中证实是一种优良的催化剂，生成了99%立体选择性的d-薄荷基顺式-2-苯基-环丙烷-1-羧酸盐。
• Asymmetric Reactions Catalyzed by Chiral Metal Complexes. L. Synthesis of atropisomeric biphenylbisphosphine, 6,6'-bis(dicyclohexylphosphino)-3,3'-dimethoxy-2,2',4,4'-tetramethyl-1,1'-biphenyl and its use in rhodium(I)-catalyzed asymmetric hydrogenation.
  作者：Masanao MURATA、Naoko YAMAMOTO、Kiyoshi YOSHIKAWA、Toshiaki MORIMOTO、Kazuo ACHIWA

  DOI：10.1248/cpb.39.2767

  日期：——

  An optically pure atropisomeric biphenylbisphosphine, Cy-BIMOP, has been prepared, and its rhodium(I) complex showed higher catalytic activity and better enantioselectivity with the reverse configuration than BIMOP, p-MeO-BIMOP, and BINAP in the asymmetric hydrogentions of (Z)-α-acetamidoxinnamic acid, itaconic acid, and its derivative.

  与 BIMOP、p-MeO-BIMOP 和 BINAP 相比，在 (Z)-α-乙脒肉桂酸、衣康酸及其衍生物的不对称加氢反应中，制备了一种光学纯的异构体联苯双膦 Cy-BIMOP，其铑（I）配合物显示出更高的催化活性和更好的反构型对映体选择性。
• Preparation of Axially Chiral Biphenyl Diphosphine Ligands and Their Application in Asymmetric Hydrogenation
  作者：Toshiaki Morimoto、Kiyoshi Yoshikawa、Masanao Murata、Naoko Yamamoto、Kazuo Achiwa

  DOI：10.1248/cpb.52.1445

  日期：——

  reduction, methoxylation through diazotization, Ullmann coupling, bromination, phosphorylation, optical resolution, and silane reduction, and the obtained ligands were used in rhodium-catalyzed asymmetric hydrogenation.

  从2,6-二甲基硝基苯开始，对映体纯的形式通过8个步骤制备带有对映体纯形式的轴向手性联苯基二苯基二膦配体：碘化，还原，通过重氮化进行甲氧基化，Ullmann偶联，溴化，磷酸化，旋光拆分，硅烷还原，所得配体用于铑催化的不对称加氢反应。
• A new type of atropisomeric biphenylbisphosphine ligand, (R)-MOC-BIMOP and its use in efficient asymmetric hydrogenation of α-aminoketone and itaconic acid
  作者：Kiyoshi Yoshikawa、Naoko Yamamoto、Masanao Murata、Katsuya Awano、Toshiaki Morimoto、Kazuo Achiwa

  DOI：10.1016/s0957-4166(00)82304-6

  日期：1992.1

  A new atropisomeric biphenylbisphosphine, MOC-BIMOP, has been prepared in enantiomerically pure form and its rhodium(I) complex proved to be an efficient catalyst in the asymmetric hydrogenations of alpha-aminoketone hydrochloride and itaconic acid. A possible mechanism of our origin has been described for the hydrogenations.
• Synthesis of axially dissymmetric biphenylbisphosphine ligands, bimops and asymmetric hydrogenations of .BETA.-keto ester and .ALPHA.,.BETA.-unsaturated carboxylic acid catalyzed by their ruthenium (II) complexes.
  作者：Naoko YAMAMOTO、Masanao MURATA、Toshiaki MORIMOTO、Kazuo ACHIWA

  DOI：10.1248/cpb.39.1085

  日期：——

  Axially dissymmetric biphenylbisphosphine ligands, BIMOP (1a) and p-MeO-BIMOP (1b) have been newly designed and prepared. The ruthenium (II) complexes of (R)-1a and 1b proved to be excellent catalysts in asymmetric hydrogenations of methyl 3-oxobutanoate and tiglic acid affording (R)-methyl 3-hydroxybutanoate of 95-99 % ee and (R)-2-methylbutyric acid of 86-91 % ee, respectively.

  新设计并合成了轴向非对称的双联苯双膦配体BIMOP（1a）和p-MeO-BIMOP（1b）。通过实验证实，钌(II)配合物(R)-1a和1b在甲基3-氧代丁酸酯和变性腺苷酸不对称氢化中是出色的催化剂，分别得到对映体纯度为95-99%的(R)-甲基3-羟基丁酸酯和86-91%的(R)-2-甲基丁酸。