| 204461-66-5

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• CAS: 204461-66-5
• 化学式: C₃₆H₅₂CuN₂O₂
• 分子量: 608.367
• InChiKey: QVLHQNLXGXYWCJ-CITKKJEGSA-L

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：

  在 thianthrenyl hexafluoroantimonate 作用下， 以 二氯甲烷 为溶剂， 生成
  参考文献：
  名称：

  Electrochemical and Spectroscopic Effects of Mixed Substituents in Bis(phenolate)–Copper(II) Galactose Oxidase Model Complexes

  摘要：

  Nonsymmetric substitution of salen (1(R1,R2)) and reduced salen (2(R1,R2)) Cu-II-phenoxyl complexes with a combination of -Bu-t, -(SPr)-Pr-i, and -OMe substituents leads to dramatic differences in their redox and spectroscopic properties, providing insight into the influence of the cysteine-modified tyrosine cofactor in the enzyme galactose oxidase (GO). Using a modified Marcus-Hush analysis, the oxidized copper complexes are characterized as Class II mixed-valent due to the electronic differentiation between the two substituted phenolates. Sulfur K-edge X-ray absorption spectroscopy (XAS) assesses the degree of radical delocalization onto the single sulfur atom of nonsymmetric [1(tBu,SMe)](+) at 7%, consistent with other spectroscopic and electrochemical results that suggest preferential oxidation of the -SMe bearing phenolate. Estimates of the thermodynamic free energy difference between the two localized states (Delta G degrees) and reorganizational energies (lambda(R1R2)) of [1(R1,R2)](+) and [2(R1,R2)](+) lead to accurate predictions of the spectroscopically observed IVCT transition energies. Application of the modified Marcus-Hush analysis to GO using parameters determined for [2(R1,R2)](+) predicts a nu(max) of similar to 43600 cm(-1), well within the energy range of the broad Vis-NIR band displayed by the enzyme.

  DOI：

  10.1021/ja211247f
• 作为产物：
  描述：

  (R,R)-N,N'-bis(3,5-di-tert-butylsalicylidene)-1,2-cyclohexanediamine 、 copper diacetate 以 甲醇 为溶剂， 反应 0.08h， 以83%的产率得到
  参考文献：
  名称：

  Salen配体和Pd（II）–和Cu（II）–Salen配合物的无溶剂合成：在将α-四氢萘酮氧化为α-萘酚中的用途

  摘要：

  摘要 在不存在溶剂的情况下，通过手动研磨试剂，使外消旋的反式-环己烷-1，2-二胺与十一种在芳香环上具有不同取代方式的醛反应。在仅10分钟的反应中，以中等到高的化学产率获得了相应的亚胺。一锅两步制备选定的亚胺与Pd（OAc）2和Cu（OAc）2的稳定配合物，并将这些配合物用作甲基1-氧代-1,2,3芳构化的催化剂，还报道了4-四氢萘-2-羧酸酯为相应的1-羟基萘-2-羧酸甲酯。 在不存在溶剂的情况下，通过手动研磨试剂，使外消旋的反式-环己烷-1，2-二胺与十一种在芳香环上具有不同取代方式的醛反应。在仅10分钟的反应中，以中等到高的化学产率获得了相应的亚胺。一锅两步制备选定的亚胺与Pd（OAc）2和Cu（OAc）2的稳定配合物，并将这些配合物用作甲基1-氧代-1,2,3芳构化的催化剂，还报道了4-四氢萘-2-羧酸酯为相应的1-羟基萘-2-羧酸甲酯。

  DOI：

  10.1055/s-0036-1588446
• 作为试剂：
  描述：

  2-溴-4-甲基苯酚 在 N-羟基邻苯二甲酰亚胺 、 cobalt(II) chloride hexahydrate 、 [CuC₆H₁₀(NCHC₆H₂O(C(CH₃)3)2)2] 、 氧气 、 sodium hydroxide 作用下， 以 甲醇 为溶剂， 65.0 ℃ 、101.33 kPa 条件下， 反应 7.0h， 以50.7%的产率得到3-溴-4-羟基苯甲醛
  参考文献：
  名称：

  Aerobic oxidation of p-cresols to 4-hydroxy benzaldehydes catalyzed by cobaltous chloride/NHPI/salen-Cu(II) catalytic system

  摘要：

  首次研究了以大气分子氧为氧化剂，以氯化钴和 N-羟基邻苯二甲酰亚胺（NHPI）组合为催化剂，在甲醇中将 2-甲氧基对甲酚、对甲酚、2-溴对甲酚氧化成相应的 4-羟基苯甲醛的过程。结果表明，反应的进展与底物结构中的取代基有关：供电子基团甲氧基有利于有氧反应，而夺电子基团 Br 则不利于反应。在氯化钴/NHPI 催化体系中引入柳铜(II)配合物作为第三组分，可以大大改善对甲酚和 2-溴-对甲酚的有氧氧化反应，将其转化为相应的 4-羟基苯甲醛。

  DOI：

  10.1007/s11164-013-1494-4

文献信息

• Mechanistic Insights from Reactions between Copper(II)−Phenoxyl Complexes and Substrates with Activated C−H Bonds
  作者：Russell C. Pratt、T. Daniel P. Stack

  DOI：10.1021/ic048695i

  日期：2005.4.1

  mechanisms: one proceeds by a simple bimolecular reaction, while the other first enters into a substrate-binding equilibrium before subsequently reacting by an intramolecular reaction. The reactions proceeding by the latter mechanism have faster overall rates, which correlates to a lower entropic barrier for the substrate-binding mechanism. Correlation of the reaction rates with the C-H bond dissociation

  使用底物苯甲醇和9,10-二氢蒽研究了金属酶半乳糖氧化酶的氧化活性形式的两种铜（II）-苯氧基类似物[1tBu2] +和[2tBu2] +的反应性。总共四个反应。在所有情况下，反应化学计量比表明氧化剂与苯甲醛或蒽产物的比例为2：1，表明[1tBu2] +和[2tBu2] +最终仅表现为单电子氧化剂，但反应动力学均表明仅一种电子氧化剂速率确定步骤涉及铜（II）-苯氧基配合物。对于每种底物，速率定律表明[1tBu2] +和[2tBu2] +通过不同的机理反应：一种通过简单的双分子反应进行，而另一种首先进入底物结合平衡，然后随后通过分子内反应进行反应。通过后一种机理进行的反应具有更快的总速率，这与底物结合机理的较低的熵垒有关。反应速率与底物的CH键解离能以及显着的氘动力学同位素效应的相关性表明，速率确定步骤涉及从活化的CH键中提取氢原子。[1tBu2] + /苯甲醇反应的非经典KIE的可变温度研究（268-308
• 一种7-酮-胆固醇乙酸酯的制备方法
  申请人：上海创诺医药集团有限公司

  公开号：CN113024625A

  公开（公告）日：2021-06-25

  本发明涉及一种7‑酮‑胆固醇乙酸酯的制备方法。具体地，本发明所述方法以胆固醇乙酸酯为原料，以Salen Cu(II)为催化剂，以空气或纯氧为氧化剂，高收率、高纯度、工艺简单、低成本地制得了所述7‑酮‑胆固醇乙酸酯。
• Visualizing Diastereomeric Interactions of Chiral Amine–Chiral Copper Salen Adducts by EPR Spectroscopy and DFT
  作者：Damien M. Murphy、Ignacio Caretti、Emma Carter、Ian A. Fallis、Marcus C. Göbel、James Landon、Sabine Van Doorslaer、David J. Willock

  DOI：10.1021/ic200113u

  日期：2011.8

  Single enantiomers of R/S-methylbenzylamine (MBA) were found to selectively form adducts with two chiral Cu-salen complexes, [Cu-II(1)] (H(2)1 = N,N'-bis(3,5-ditert-butylsalicylidene)-1,2-diaminocyclohexane) and [Cu-II(2)] (H(2)2 = N,N'-bis-salicylidene-1,2-cyclohexanediamino). The axial g/A spin Hamiltonian parameters of the Cu-MBA adducts were typical of 5-coordinate species. Enantiomer discrimination in the MBA binding was directly evidenced by W-band CW EPR, revealing an 86 +/- 5% preference for formation of the R,R-[Cu(1)] + S-MBA adducts compared to R,R-[Cu(1)] + R-MBA; this was reduced to a 57 +/- 5% preference for R,R-[Cu(2)] + S-MBA following removal of the rert-butyl groups. The structure of these diastereomeric adducts was further probed by different hyperfine techniques (ENDOR and HYSCORE), although no structural differences were detected between these adducts using these techniques. The diastereomeric adducts were found to possess lower symmetry, as evidenced by rhombic g tensors and inequivalent H-imine couplings. This was caused by the selective binding mode of MBA onto one side of the chiral Cu-II complex. DFT calculations were performed on the R,R-[Cu(1)] + S-MBA and R,R-[Cu(1)] + R-MBA adducts. A distinct difference in orientation and binding mode of the MBA was identified in,both adducts, confirming the experimental results. The preferred heterochiral R,R-[Cu(1)] + S-MBA adduct was found to be 5 kJ mol(-1) lower in energy compared to the homochiral adduct. A delicate balance of steric repulsion between the alpha-proton (attached to the asymmetric carbon atom) of MBA and the methine proton (attached to the asymmetric carbon atom) of [Cu(1)] was crucial in the stereoselective binding.