4,5,6-trimethyl-5',6'-benzo-2,2'-cyclo[(2S,4S)-pentadioxy] biphenyle

• 分子结构分类: 有机化合物 - 苯类化合物 - 萘
• 英文名称: 4,5,6-trimethyl-5',6'-benzo-2,2'-cyclo[(2S,4S)-pentadioxy] biphenyle
• 英文别名: 1-(6-Hydroxy-2,3,4-trimethylphenyl)naphthalen-2-ol；1-(6-hydroxy-2,3,4-trimethylphenyl)naphthalen-2-ol
• 化学式: C₁₉H₁₈O₂
• 分子量: 278.351
• InChiKey: QSJPSIRVZGKUEO-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.2
• 重原子数：
  21
• 可旋转键数：
  1
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.16
• 拓扑面积：
  40.5
• 氢给体数：
  2
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  4,5,6-trimethyl-5',6'-benzo-2,2'-cyclo[(2S,4S)-pentadioxy] biphenyle 在 1,2-双(二苯基膦)乙烷氯化镍 吡啶 、 三乙烯二胺 作用下， 以 二氯甲烷 、 N,N-二甲基甲酰胺 为溶剂， 反应 88.0h， 生成 {2-[2-(Diphenyl-phosphinoyl)-naphthalen-1-yl]-3,4,5-trimethyl-phenyl}-diphenyl-phosphane
  参考文献：
  名称：

  New developments in the synthesis of heterotopic atropisomeric diphosphines via diastereoselective aryl coupling reactions

  摘要：

  The new heterotopic atropisomeric diphosphine (R)-5,6-benzo-2,2'-bis(diphenylphosphino)-4',5',6'-trimethylbiphenyl has been prepared. The key step of this synthesis is a diastereoselective intramolecular aryl-aryl coupling reaction via oxidation of a suitable, chiral diarylcuprate. The catalytic properties of the diphosphine in ruthenium promoted hydrogenations of model substrates and in rhodium promoted 1,4-additions of boronic acids to alpha,beta-unsaturated ketones are fully comparable to those of reference ligands such as BINAP. This seems to indicate that C-2-symmetry is not a structural prerequisite for atropisomeric chiral diphosphines to obtain high enantio selectivities in 1,4-addition reactions as well as in hydrogenation reactions. (C) 2004 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetasy.2004.05.014
• 作为产物：
  描述：

  3,4,5-三甲基苯酚 在 N-溴代丁二酰亚胺(NBS) 、 偶氮二甲酸二异丙酯 、 仲丁基锂 、 三溴化硼 、 三苯基膦 作用下， 以 四氢呋喃 、 正己烷 、 二氯甲烷 、 N,N-二甲基甲酰胺 为溶剂， 反应 30.0h， 生成 4,5,6-trimethyl-5',6'-benzo-2,2'-cyclo[(2S,4S)-pentadioxy] biphenyle
  参考文献：
  名称：

  New developments in the synthesis of heterotopic atropisomeric diphosphines via diastereoselective aryl coupling reactions

  摘要：

  The new heterotopic atropisomeric diphosphine (R)-5,6-benzo-2,2'-bis(diphenylphosphino)-4',5',6'-trimethylbiphenyl has been prepared. The key step of this synthesis is a diastereoselective intramolecular aryl-aryl coupling reaction via oxidation of a suitable, chiral diarylcuprate. The catalytic properties of the diphosphine in ruthenium promoted hydrogenations of model substrates and in rhodium promoted 1,4-additions of boronic acids to alpha,beta-unsaturated ketones are fully comparable to those of reference ligands such as BINAP. This seems to indicate that C-2-symmetry is not a structural prerequisite for atropisomeric chiral diphosphines to obtain high enantio selectivities in 1,4-addition reactions as well as in hydrogenation reactions. (C) 2004 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetasy.2004.05.014

文献信息

• キラルジホスフィン及びその金属錯体
  申请人：——

  公开号：JP2004513951A

  公开（公告）日：2004-05-13

  The present invention is directed to novel chiral diphosphines (R) or (S) and their use as optically active ligands for preparing diphosphine-metal complexes. The present invention also relates to a diphosphine-metal complex containing the chiral diphosphine (R) or (S), and to the use of the diphosphine-metal complex as a catalyst in a method for asymmetric catalysis of an unsaturated compound having a functional group. .

  本发明涉及新型手性二膦（R）或（S）及其用作光学活性配体，用于制备二膦金属配合物。本发明还涉及包含手性二膦（R）或（S）的二膦金属配合物，以及将该二膦金属配合物用作催化剂，在不饱和化合物具有功能基团的不对称催化方法中的应用。
• New developments in the synthesis of heterotopic atropisomeric diphosphines via diastereoselective aryl coupling reactions
  作者：Jonathan Madec、Guillaume Michaud、Jean-Pierre Genêt、Angela Marinetti

  DOI：10.1016/j.tetasy.2004.05.014

  日期：2004.7

  The new heterotopic atropisomeric diphosphine (R)-5,6-benzo-2,2'-bis(diphenylphosphino)-4',5',6'-trimethylbiphenyl has been prepared. The key step of this synthesis is a diastereoselective intramolecular aryl-aryl coupling reaction via oxidation of a suitable, chiral diarylcuprate. The catalytic properties of the diphosphine in ruthenium promoted hydrogenations of model substrates and in rhodium promoted 1,4-additions of boronic acids to alpha,beta-unsaturated ketones are fully comparable to those of reference ligands such as BINAP. This seems to indicate that C-2-symmetry is not a structural prerequisite for atropisomeric chiral diphosphines to obtain high enantio selectivities in 1,4-addition reactions as well as in hydrogenation reactions. (C) 2004 Elsevier Ltd. All rights reserved.