chloro{4-(N-2',6'-dimethylphenyl)imino­me­thyl­[2.2]­­pa­racyclophan-5-yl-C,N}(triphenyl­phos­phine-P)pal­ladi­um­(II) | 1190405-63-0

• 英文名称: chloro{4-(N-2',6'-dimethylphenyl)imino­me­thyl­[2.2]­­pa­racyclophan-5-yl-C,N}(triphenyl­phos­phine-P)pal­ladi­um­(II)
• 英文别名: chloro{5-[N-(2',6'-dimethylphenyl)iminomethyl][2.2]paracyclophan-4yl-C,N}(triphenylphosphine-P)palladium(II)
• CAS: 1190405-63-0
• 化学式: C₄₃H₃₉ClNPPd
• 分子量: 742.636
• InChiKey: WNYAHHPHCMQNPL-DVSHGQQWSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
  None
• 可旋转键数：
  None
• 环数：
  None
• sp3杂化的碳原子比例：
  None
• 拓扑面积：
  None
• 氢给体数：
  None
• 氢受体数：
  None

反应信息

• 作为反应物：
  描述：

  chloro{4-(N-2',6'-dimethylphenyl)imino­me­thyl­[2.2]­­pa­racyclophan-5-yl-C,N}(triphenyl­phos­phine-P)pal­ladi­um­(II) 、 potassium iodide 以 甲醇 为溶剂， 反应 2.0h， 以85%的产率得到iodo{4-(N-2',6'-dimethylphenyl)imino­me­thyl­[2.2]­­pa­racyclophan-5-yl-C,N}(triphenyl­phos­phine-P)pal­ladi­um­(II)
  参考文献：
  名称：

  平面手性 CN-钯环对 Suzuki 反应的对映选择性催化：两个催化循环的竞争

  摘要：

  手性 CN-钯环催化阻转选择性 Suzuki 反应的研究表明，在该过程中存在两个相互竞争的催化循环，每个循环的相对贡献取决于催化剂的结构和反应条件。当使用非茂金属平面手性亚胺化 CN-二聚体作为催化剂时，非质子介质中的反应主要遵循保留钯环结构的路径，从而提供高达 53% ee 的对映选择性。反应完成后回收的 μ-碘化物环钯 CN-二聚体的结构通过其三苯基膦衍生物的 X 射线衍射和光谱研究得到证实。

  DOI：

  10.1007/s11172-017-1729-4

文献信息

• Evidence on palladacycle-retaining pathway for Suzuki coupling. Inapplicability of Hg-drop test for palladacycle catalysed reactions
  作者：Ol'ga N. Gorunova、Michail V. Livantsov、Yuri K. Grishin、Michail M. Ilyin、Konstantin A. Kochetkov、Andrei V. Churakov、Lyudmila G. Kuz'mina、Victor N. Khrustalev、Valery V. Dunina

  DOI：10.1016/j.jorganchem.2013.03.050

  日期：2013.8

  Investigation of the model atroposelective Suzuki reaction catalysed by chiral CN-palladacycles have shown that two types of catalytic cycle may operate simultaneously, with strong dependence of their contributions upon the palladacycle structure and conditions used. Dominant contribution of palladacycle retaining pathway was provided by the non-metallocene planar chiral iminate CN-palladacycle (R-pl)-4a using as catalyst, in reaction performed in toluene under aerobic conditions with KF as a base, affording (S-a)-2-methoxy-1,1'-binaphthalene with enantioselectivity up to 53% ee. The catalyst was recovered almost quantitatively as an iodide-bridged dimer, whose structure was confirmed by an X-ray diffraction study of its phosphine derivative. It was also shown that the common Hg drop test was unsuitable for mechanistic testing of palladacycle-catalysed reactions because of the transmetallation product formation, whose structure was confirmed by an X-ray diffraction study. (C) 2013 Elsevier B.V. All rights reserved.