rac-4-bromo[2.2]paracyclophan-13-ylenediphenylphosphine | 1062306-89-1

• 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: rac-4-bromo[2.2]paracyclophan-13-ylenediphenylphosphine
• 英文别名: 4-bromo-12-diphenylphosphino[2.2]paracyclophane；(11-Bromo-5-tricyclo[8.2.2.24,7]hexadeca-1(12),4,6,10,13,15-hexaenyl)-diphenylphosphane
• CAS: 1062306-89-1；727419-33-2
• 化学式: C₂₈H₂₄BrP
• 分子量: 471.376
• InChiKey: MWPTWTBWNOLSAE-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7.8
• 重原子数：
  30
• 可旋转键数：
  3
• 环数：
  8.0
• sp3杂化的碳原子比例：
  0.14
• 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：

  rac-4-bromo[2.2]paracyclophan-13-ylenediphenylphosphine 在 lithium aluminium tetrahydride 、 正丁基锂 、 三溴化磷 作用下， 以 四氢呋喃 、 二氯甲烷 、 甲苯 、 正戊烷 为溶剂， 反应 73.0h， 生成 3-(4-diphenylphosphino[2.2]paracyclophan-12-ylmethyl)-1-phenylimidazolium 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：

  4,12-dibromo[2.2]paracyclophane 、 二苯基氯化膦 在 正丁基锂 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 反应 2.0h， 以90%的产率得到rac-4-bromo[2.2]paracyclophan-13-ylenediphenylphosphine
  参考文献：
  名称：

  用于芳基氯化物酰胺化的不对称双膦：动力学研究

  摘要：

  研究了在不对称双膦存在下钯催化的 4-氯甲苯与苯甲酰胺酰胺化的速率决定步骤。通过动力学研究，研究了具有二环己基膦基和二芳基膦基的同构 [2.2] 对环芳衍生的双膦作为氧化加成和还原消除中的配体。当应用含有富电子膦基团和释放电子较少的膦基部分的双膦配体时，还原消除会加速。除了还原消除之外，金属转移对钯催化的芳基卤化物的酰胺化影响最大。

  DOI：

  10.1002/ejoc.201400159

文献信息

• [2.2]Paracyclophane-Derived Chiral P,N-Ligands: Design, Synthesis, and Application in Palladium-Catalyzed Asymmetric Allylic Alkylation
  作者：Biao Jiang、Yang Lei、Xiao-Long Zhao

  DOI：10.1021/jo801373r

  日期：2008.10.3

  2]paracyclophane-derived P,N-ligands were designed and synthesized. A full investigation of the relationship between the ligands' structures and their abilities to induce asymmetry in palladium-catalyzed asymmetric allylic alkylations of malonates with 1,3-diphenyl 2-propenyl acetate was carried out, and high yields and enantioselectivities (i.e., 99% yield, 97% ee) were observed while using ligands bearing

  以调整结构的柔性和刚度的想法，设计并合成了几种[2.2]对环芳烃衍生的P，N-配体。全面研究了配体结构及其在钯催化的1,3-二苯基2-丙烯基丙二酸丙二酸酯的钯催化不对称烯丙基烷基化反应中诱导不对称性之间的关系，并获得了高收率和对映选择性（即99％当使用具有匹配的平面和中心手性的配体时，观察到97％ee）。
• 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.
• Unsymmetrical Bisphosphines for the Amidation of Aryl Chlorides: A Kinetic Study
  作者：Florian C. Falk、Peter Oechsle、Werner R. Thiel、Constantin-Gabriel Daniliuc、Jan Paradies

  DOI：10.1002/ejoc.201400159

  日期：2014.6

  palladium-catalyzed amidation of 4-chlorotoluene with benzamide in the presence of unsymmetrical bisphosphines was investigated. Isostructural [2.2]paracyclophane-derived bisphosphines bearing dicyclohexylphosphino and diarylphosphino moieties were investigated as ligands in the oxidative addition and reductive elimination by kinetic studies. The reductive elimination was accelerated when a bisphosphine ligand

  研究了在不对称双膦存在下钯催化的 4-氯甲苯与苯甲酰胺酰胺化的速率决定步骤。通过动力学研究，研究了具有二环己基膦基和二芳基膦基的同构 [2.2] 对环芳衍生的双膦作为氧化加成和还原消除中的配体。当应用含有富电子膦基团和释放电子较少的膦基部分的双膦配体时，还原消除会加速。除了还原消除之外，金属转移对钯催化的芳基卤化物的酰胺化影响最大。