12-bromomethyl-4-diphenylthiophosphino[2.2]paracyclophane | 727419-41-2

• 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: 12-bromomethyl-4-diphenylthiophosphino[2.2]paracyclophane
• 英文别名: [11-(Bromomethyl)-5-tricyclo[8.2.2.24,7]hexadeca-1(12),4,6,10,13,15-hexaenyl]-diphenyl-sulfanylidene-lambda5-phosphane；[11-(bromomethyl)-5-tricyclo[8.2.2.24,7]hexadeca-1(12),4,6,10,13,15-hexaenyl]-diphenyl-sulfanylidene-λ5-phosphane
• CAS: 727419-41-2
• 化学式: C₂₉H₂₆BrPS
• 分子量: 517.469
• InChiKey: HNWLDVXKSWWLCY-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  8.8
• 重原子数：
  32
• 可旋转键数：
  4
• 环数：
  8.0
• sp3杂化的碳原子比例：
  0.17
• 拓扑面积：
  32.1
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  12-bromomethyl-4-diphenylthiophosphino[2.2]paracyclophane 在 镍 作用下， 以 N,N-二甲基甲酰胺 、 乙腈 为溶剂， 反应 48.0h， 生成 3-(4-diphenylphosphino[2.2]paracyclophan-12-ylmethyl)-1-(2,6-diisopropylphenyl)imidazolium bromide
  参考文献：
  名称：

  Synthesis of iridium complexes with new planar chiral chelating phosphinyl-imidazolylidene ligands and their application in asymmetric hydrogenation

  摘要：

  The synthesis of planar chiral phosphinoimidazolium salts such as (R-p)-3-(4-diphenyl-phosphino[2.2]paracyclophan-12-ylmethyl)-1-(2,6-diisopropylphenyl)imidazolium bromide (R-p)-11c starting from enantiopure 4,12-dibromo[2.2]paracyclophane (R-p)-6 is reported. After deprotonation of these salts and a subsequent reaction with [Ir(COD)Cl](2), chelating iridium imidazolylidene complexes (R-p)-5a-c are obtained. These complexes catalyze the asymmetric hydrogenation of functionalized and simple alkenes with up to 89% ee. (C) 2004 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetasy.2004.03.047
• 作为产物：
  描述：

  rac-4-bromo[2.2]paracyclophan-13-ylenediphenylphosphine 在 lithium aluminium tetrahydride 、 正丁基锂 、 sulfur 作用下， 以 四氢呋喃 、 二氯甲烷 、 正戊烷 为溶剂， 反应 3.0h， 生成 12-bromomethyl-4-diphenylthiophosphino[2.2]paracyclophane
  参考文献：
  名称：

  Synthesis of iridium complexes with new planar chiral chelating phosphinyl-imidazolylidene ligands and their application in asymmetric hydrogenation

  摘要：

  The synthesis of planar chiral phosphinoimidazolium salts such as (R-p)-3-(4-diphenyl-phosphino[2.2]paracyclophan-12-ylmethyl)-1-(2,6-diisopropylphenyl)imidazolium bromide (R-p)-11c starting from enantiopure 4,12-dibromo[2.2]paracyclophane (R-p)-6 is reported. After deprotonation of these salts and a subsequent reaction with [Ir(COD)Cl](2), chelating iridium imidazolylidene complexes (R-p)-5a-c are obtained. These complexes catalyze the asymmetric hydrogenation of functionalized and simple alkenes with up to 89% ee. (C) 2004 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetasy.2004.03.047

文献信息

• Synthesis of iridium complexes with new planar chiral chelating phosphinyl-imidazolylidene ligands and their application in asymmetric hydrogenation
  作者：Thilo Focken、Gerhard Raabe、Carsten Bolm

  DOI：10.1016/j.tetasy.2004.03.047

  日期：2004.6

  The synthesis of planar chiral phosphinoimidazolium salts such as (R-p)-3-(4-diphenyl-phosphino[2.2]paracyclophan-12-ylmethyl)-1-(2,6-diisopropylphenyl)imidazolium bromide (R-p)-11c starting from enantiopure 4,12-dibromo[2.2]paracyclophane (R-p)-6 is reported. After deprotonation of these salts and a subsequent reaction with [Ir(COD)Cl](2), chelating iridium imidazolylidene complexes (R-p)-5a-c are obtained. These complexes catalyze the asymmetric hydrogenation of functionalized and simple alkenes with up to 89% ee. (C) 2004 Elsevier Ltd. All rights reserved.