(S)-6,6'-dimethyl-2,2'-bis(diphenylphosphinamino)biphenyl | 86514-04-7

• 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: (S)-6,6'-dimethyl-2,2'-bis(diphenylphosphinamino)biphenyl
• 英文别名: N-diphenylphosphanyl-2-[2-(diphenylphosphanylamino)-6-methylphenyl]-3-methylaniline
• CAS: 86514-04-7；121772-80-3
• 化学式: C₃₈H₃₄N₂P₂
• 分子量: 580.649
• InChiKey: ANMGZOKKWOBDHY-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  8.89
• 重原子数：
  42.0
• 可旋转键数：
  9.0
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.05
• 拓扑面积：
  24.06
• 氢给体数：
  2.0
• 氢受体数：
  2.0

反应信息

• 作为反应物：
  描述：

  dichloro(1,5-cyclooctadiene)ruthenium(II) 、 (S)-6,6'-dimethyl-2,2'-bis(diphenylphosphinamino)biphenyl 以 甲醇 为溶剂， 生成 dichlorto-(S)-6,6'-dimethyl-2,2'-bis(diphenylphosphinoamino)biphenyl-ruthenium(II)
  参考文献：
  名称：

  Preparation and use of a chiral amine ruthenium hydrogenation catalyst supported on mesoporous silica

  摘要：

  We report the synthesis and use of dichloro-(S)-6,6'-dimethyl-2,2'-diaminobiphenyl-ruthenium complex ((S)-MAB-Ru), an air-stable, highly active catalyst for the hydrogenation of alpha, beta-unsaturated carboxylic acids at 25degreesC and 4.85 atm, hydrogen. The homogeneous hydrogenations of itaconic acid and alpha-acetamidocinnamic acid had yields above 97% in each case, and the enantiomeric excesses (e.e.) were 80 and 69.8% to the (R)-products, respectively. When we used (S)-MAB-Ru chemically bound to MCM-41, a mesoporous SiO2, the conversion of both acids was complete and both e.e. were practically 97%. The solid-bound catalyst was successfully reutilized in the hydrogenation of itaconic acid and the drop in asymmetric induction was only 3% after three runs. The fact that complexes containing chiral amine ligands provide such high yields and e.e. opens a potentially important area of research in the design of industrially relevant catalysts. (C) 2002 Elsevier Science B.V. All rights reserved.

  DOI：

  10.1016/s1381-1169(02)00654-4
• 作为产物：
  描述：

  (S)-(-)-6,6'-二甲基-2,2'-联苯二胺 在 三乙胺 作用下， 以 苯 为溶剂， 反应 7.0h， 生成 (S)-6,6'-dimethyl-2,2'-bis(diphenylphosphinamino)biphenyl
  参考文献：
  名称：

  NEW ATROPISOMERIC CHIRAL BISPHOSPHINE, (S)-6,6′-DIMETHYL-2,2′-BIS(DIPHENYLPHOSPHINAMINO)BIPHENYL, AND ASYMMETRIC HYDROGENATION USING THE Rh(I) COMPLEX THEREOF

  摘要：

  新制备了异构手性双膦--(S)-6,6′-二甲基-2,2′-双（二苯基膦氨基）联苯（MABP），并发现其 Rh（I）配合物在 0°C 以下温度、1 atm 的氢压条件下对 2-乙酰氨基丙烯酸的不对称氢化非常有效。

  DOI：

  10.1246/cl.1983.441

文献信息

• Axially Dissymmetric Bis(triaryl)phosphines in the Biphenyl series: Synthesis of (6,6′-dimethylbiphenyl-2,2′-diyl)bis(diphenylphosphine) (‘BIPHEMP’) and analogues, and their use in Rh(I)-catalyzed asymmetric isomerizations of<i>N,N</i>-diethylnerylamine
  作者：Rudolf Schmid、Marco Cereghetti、Bernd Heiser、Peter Schönholzer、Hans-Jürgen Hansen

  DOI：10.1002/hlca.19880710427

  日期：1988.6.15

  free diphosphine and of the derived Rh(I) complex, and for (−)-(R)- 13 by X-ray analysis of the derived Rh(I) complex. Configurational assignments for the substituted BIPHEMP analogues 1112 were achieved by means of 1H-NMR comparisons. The BIPHEMP ligand 10 and analogues 11, 12 and 13 are the first examples of optically active bis(triaylphosphines) containing the axially dissymmetric biphenyl moiety

  轴向不对称二膦（-）-（R）-和（+）-（S）-（6-6'-二甲基联苯-2,2'-二基）双（二苯基膦）（（-）-（R） -（10）和（+）-（S）-10 ;'BIPHEMP'）是从（R）-和（S）-6,6'-二甲基联苯-2,2'-二胺（（R）-和（S）-16）分别通过Sandmeyer反应，锂化和次膦酰基化。此外，外消旋的4,4'-二甲基-和4,4'-双（二甲基氨基）取代的类似物11和12分别合成了6,6'-桥接的类似物1,11-双（二苯基膦基）-5,7-二氢二苯并[ c，e ] oxepin （13）并拆分为光学纯的（R）-和（S）-对映异构体通过与二μ-chlorob络合是（[R）-2- [1-（二甲基氨基）乙基] pheny- ç ñ }二钯（II）（（- [R ）- 18）。二膦（S）-10和（R）-13以及两种衍生的阳离子Rh（I）配合物[Rh（（S）-10）（nbd）] BF
• SCHMID, RUDOLF;CEREGHETTI, MARCO;HELSER, BERND;SCHONHOLZER, PETER;HANSEN,+, HELV. CHIM. ACTA, 71,(1988) N 4, 897-929
  作者：SCHMID, RUDOLF、CEREGHETTI, MARCO、HELSER, BERND、SCHONHOLZER, PETER、HANSEN,+

  DOI：——

  日期：——
• NEW ATROPISOMERIC CHIRAL BISPHOSPHINE, (<i>S</i>)-6,6′-DIMETHYL-2,2′-BIS(DIPHENYLPHOSPHINAMINO)BIPHENYL, AND ASYMMETRIC HYDROGENATION USING THE Rh(I) COMPLEX THEREOF
  作者：Akira Uehara、Tohru Kubota、Ryokichi Tsuchiya

  DOI：10.1246/cl.1983.441

  日期：1983.4.5

  Atropisomeric chiral bisphosphine, (S)-6,6′-dimethyl-2,2′-bis(diphenylphosphinamino)biphenyl (MABP) was newly prepared, and the Rh(I) complex thereof was found to be highly effective for the asymmetric hydrogenation of 2-acetamidoacrylic acid even under 1 atm of hydrogen pressure at a temperature below 0°C.

  新制备了异构手性双膦--(S)-6,6′-二甲基-2,2′-双（二苯基膦氨基）联苯（MABP），并发现其 Rh（I）配合物在 0°C 以下温度、1 atm 的氢压条件下对 2-乙酰氨基丙烯酸的不对称氢化非常有效。
• Preparation and use of a chiral amine ruthenium hydrogenation catalyst supported on mesoporous silica
  作者：Cuauhtemoc Pérez、Salud Pérez、Gustavo A Fuentes、Avelino Corma

  DOI：10.1016/s1381-1169(02)00654-4

  日期：2003.4

  We report the synthesis and use of dichloro-(S)-6,6'-dimethyl-2,2'-diaminobiphenyl-ruthenium complex ((S)-MAB-Ru), an air-stable, highly active catalyst for the hydrogenation of alpha, beta-unsaturated carboxylic acids at 25degreesC and 4.85 atm, hydrogen. The homogeneous hydrogenations of itaconic acid and alpha-acetamidocinnamic acid had yields above 97% in each case, and the enantiomeric excesses (e.e.) were 80 and 69.8% to the (R)-products, respectively. When we used (S)-MAB-Ru chemically bound to MCM-41, a mesoporous SiO2, the conversion of both acids was complete and both e.e. were practically 97%. The solid-bound catalyst was successfully reutilized in the hydrogenation of itaconic acid and the drop in asymmetric induction was only 3% after three runs. The fact that complexes containing chiral amine ligands provide such high yields and e.e. opens a potentially important area of research in the design of industrially relevant catalysts. (C) 2002 Elsevier Science B.V. All rights reserved.