17-Chloro-7-methyl-3,7,11-triazabicyclo[11.3.1]heptadeca-1(17),13,15-triene | 1259365-35-9

• 分子结构分类: 有机化合物 - 有机氮化合物
• 英文名称: 17-Chloro-7-methyl-3,7,11-triazabicyclo[11.3.1]heptadeca-1(17),13,15-triene
• 英文别名: 17-chloro-7-methyl-3,7,11-triazabicyclo[11.3.1]heptadeca-1(17),13,15-triene
• CAS: 1259365-35-9
• 化学式: C₁₅H₂₄ClN₃
• 分子量: 281.829
• InChiKey: RIFTWABDKVZQNJ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.8
• 重原子数：
  19
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.6
• 拓扑面积：
  27.3
• 氢给体数：
  2
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  17-Chloro-7-methyl-3,7,11-triazabicyclo[11.3.1]heptadeca-1(17),13,15-triene 在 [(IPr)Au(NCMe)]SbF₆ 、 sodium iodide 、 sodium bromide 作用下， 以 氘代乙腈 为溶剂， 反应 102.0h， 生成 17-(4-Chlorophenoxy)-7-methyl-3,7,11-triazabicyclo[11.3.1]heptadeca-1(17),13,15-triene
  参考文献：
  名称：

  无氧化剂 Au(I)-催化的卤化物交换和 Csp2-O 键形成反应

  摘要：

  Au 已被证明通过利用其 π 路易斯酸特性、Au(I)/Au(III) 氧化还原特性或两者的组合来介导许多有机转化。由于 Au(I)/Au(III) 对的高氧化电位，涉及 Au 的氧化还原催化通常需要使用强外部氧化剂。该研究展示了不寻常的无外部氧化剂 Au(I) 催化的卤化物交换（包括氟化）和使用模型芳基卤化物大环底物的 Csp2-O 键形成反应。此外，卤化物交换和 Csp2-O 偶联反应性也可以外推到带有单个螯合基团的底物，从而进一步了解反应机制。这项工作提供了无外部氧化剂的 Au(I) 催化碳-杂原子交叉偶联反应的第一个例子。

  DOI：

  10.1021/jacs.5b08756
• 作为产物：
  描述：

  1,3-二(溴甲基)-2-氯苯 在 氢溴酸 、 caesium carbonate 、 溶剂黄146 、 苯酚 作用下， 以 乙腈 为溶剂， 反应 72.0h， 生成 17-Chloro-7-methyl-3,7,11-triazabicyclo[11.3.1]heptadeca-1(17),13,15-triene
  参考文献：
  名称：

  Nucleophilic Aryl Fluorination and Aryl Halide Exchange Mediated by a Cu^I/Cu^III Catalytic Cycle

  摘要：

  Copper-catalyzed halide exchange reactions under very mild reaction conditions are described for the first time using a family of model aryl halide substrates. All combinations of halide exchange (I, Br, Cl, F) are observed using catalytic amounts of Cu-I. Strikingly, quantitative fluorination of aryl X substrates is also achieved catalytically at room temperature, using common F- sources, via the intermediacy of aryl-Cu-III-X species. Experimental and computational data support a redox Cu-I/Cu-III catalytic cycle involving aryl X oxidative addition at the Cu-I center, followed by halide exchange and reductive elimination steps. Additionally, defluorination of the aryl-F model system can be also achieved with Cu-I at room temperature operating under a Cu-I/Cu-III redox pair.

  DOI：

  10.1021/ja2058567

文献信息

• Catalytic C–S, C–Se, and C–P Cross-Coupling Reactions Mediated by a Cu^I/Cu^III Redox Cycle
  作者：Marc Font、Teodor Parella、Miquel Costas、Xavi Ribas

  DOI：10.1021/om3006323

  日期：2012.11.26

  A well-defined macrocyclic aryl-Cu-III complex (1) readily reacts with a series of R-SH, Ar-SH, Ar-SeH, and (RO)(2)(O)-PH (R = alkyl) nucleophiles to quantitatively afford the corresponding aryl alkyl thioethers, biaryl thioethers, biaryl selenide, and aryl dialkyl phosphonates, respectively. Competition experiments using bifunctional substrates revealed the important impact of lower pK(a) values in order to discriminate between functional groups, although other influencing parameters such as steric effects have been identified. The catalytic version of these reactions is achieved using aryl bromide and aryl chloride model substrates, affording C-S, C-Se, and C-P coupling compounds in excellent to moderate yields. Low-temperature UV-vis and NMR monitoring of the reactions of complex 1 with a variety of nucleophiles support the formation of a ground-state 1-nucleophile adduct. A mechanistic proposal for reaction of 1 with S-nucleophiles involving key nucleophile deprotonation and aryl-nucleophile reductive elimination steps is finally described.