17-Bromo-7-methyl-3,7,11-triazabicyclo[11.3.1]heptadeca-1(17),13,15-triene | 1261036-26-3

• 分子结构分类: 有机化合物 - 有机氮化合物
• 英文名称: 17-Bromo-7-methyl-3,7,11-triazabicyclo[11.3.1]heptadeca-1(17),13,15-triene
• 英文别名: 17-bromo-7-methyl-3,7,11-triazabicyclo[11.3.1]heptadeca-1(17),13,15-triene
• CAS: 1261036-26-3
• 化学式: C₁₅H₂₄BrN₃
• 分子量: 326.28
• InChiKey: GHECRDKQQVPMNL-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.9
• 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-Bromo-7-methyl-3,7,11-triazabicyclo[11.3.1]heptadeca-1(17),13,15-triene 在 [(IPr)Au(NCMe)]SbF₆ 、 四丁基氯化铵 作用下， 以 氘代乙腈 为溶剂， 反应 12.0h， 以99%的产率得到17-Chloro-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 四(乙腈)三氟甲磺酸铜(I) 、 氢溴酸 、 caesium carbonate 、 溶剂黄146 、 sodium bromide 、 苯酚 作用下， 以 乙腈 为溶剂， 反应 96.0h， 生成 17-Bromo-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

• Trifluoromethylation of a Well-Defined Square-Planar Aryl-Ni^II Complex involving Ni^III /CF₃ ^. and Ni^IV −CF₃ Intermediate Species
  作者：Mireia Rovira、Steven Roldán-Gómez、Vlad Martin-Diaconescu、Christopher J. Whiteoak、Anna Company、Josep M. Luis、Xavi Ribas

  DOI：10.1002/chem.201702168

  日期：2017.8.25

  Ni‐mediated trifluoromethylation of an aryl−Br bond in model macrocyclic ligands (Ln−Br) has been thoroughly studied, starting with an oxidative addition at Ni0 to obtain well‐defined aryl‐NiII‐Br complexes ([Ln−NiII]Br). Abstraction of the halide with AgX (X=OTf− or ClO4−) thereafter provides [Ln−NiII](OTf). The nitrate analogue has been obtained through a direct C−H activation of an aryl−H bond using NiII

  镍-介导的芳基- Br键的三氟甲基化在模型的大环配体（L Ñ -Br）已被彻底研究，开始用氧化加成在镍0，以获得良好定义的芳基-镍II -Br络合物（[L Ñ - Ni II ] Br）。与卤化银的卤化物的抽象（X =光学传递函数-或C10 4 - ）之后提供[L Ñ -Ni II ]（OTF）。硝酸盐类似物是通过使用Ni II直接对芳基-H键进行CH-H活化而获得的盐，这条路线已经通过X射线吸收光谱法（XAS）进行了研究。晶体学XRD和XAS表征表明，芳基-Ni II复合物中紧密的大环配位，这可能会阻碍与亲核试剂的直接反应。相反，观察到氧化剂具有增强的反应性，并且[L n -Ni II ]（OTf）与CF 3 +源的反应提供了L n -CF 3。产品的定量产量。实验和理论机制相结合的研究为这种转变的运作机制提供了新的见解。计算分析表明，发生了初始单电子转移（SET）到5-（三氟甲基）二苯
• Observation and Mechanistic Study of Facile CO Bond Formation between a Well‐Defined Aryl–Copper(III) Complex and Oxygen Nucleophiles
  作者：Lauren M. Huffman、Alicia Casitas、Marc Font、Mercè Canta、Miquel Costas、Xavi Ribas、Shannon S. Stahl

  DOI：10.1002/chem.201100608

  日期：2011.9.12

  adduct between 2 and the oxygen nucleophile. Collectively, kinetic and spectroscopic data support a unified mechanism for aryl‐O coupling from the CuIII complex, consisting of nucleophile coordination to the CuIII center, deprotonation of the coordinated nucleophile, and CO (or CN) reductive elimination from CuIII.

  定义明确的大环芳基-Cu III配合物（2）在温和条件下易于与各种氧亲核试剂（包括羧酸，酚和醇）反应，形成相应的芳基酯，联芳基醚和烷基芳基醚。在10 mol％Cu I存在下，大环芳基-Br物种与乙酸和对氟苯酚的反应证明了这些反应与催化CO偶联方法之间的关系。观察到芳基-Cu III - Br物种2 Br作为催化反应的中间体。化学计量的C调查O键形成反应揭示了亲核试剂依赖机制的变化。的反应2与羧酸揭示了日志（呈正相关ķ OBS）和p ķ一个亲核体的（酸性较少的亲核试剂反应更迅速），而具有最酚观察呈负相关（更酸性的酚反应更快）。后者的趋势类似于先前对氮亲核试剂的观察。使用羧酸和酸性酚，紫外可见光谱数据可支持2与氧亲核试剂之间形成基态加合物。总的来说，动力学和光谱学数据支持了Cu III进行芳基-O偶联的统一机制。复杂的，由亲核试剂的协调，以在Cu的III中心，协调亲核试剂的去质子化，和C 
• 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.
• Nucleophilic Aryl Fluorination and Aryl Halide Exchange Mediated by a Cu^I/Cu^III Catalytic Cycle
  作者：Alicia Casitas、Mercè Canta、Miquel Solà、Miquel Costas、Xavi Ribas

  DOI：10.1021/ja2058567

  日期：2011.12.7

  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.
• Oxidant-Free Au(I)-Catalyzed Halide Exchange and C_sp2–O Bond Forming Reactions
  作者：Jordi Serra、Christopher J. Whiteoak、Ferran Acuña-Parés、Marc Font、Josep M. Luis、Julio Lloret-Fillol、Xavi Ribas

  DOI：10.1021/jacs.5b08756

  日期：2015.10.21

  character, Au(I)/Au(III) redox properties or a combination of both. As a result of the high oxidation potential of the Au(I)/Au(III) couple, redox catalysis involving Au typically requires the use of a strong external oxidant. This study demonstrates unusual external oxidant-free Au(I)-catalyzed halide exchange (including fluorination) and Csp2-O bond formation reactions utilizing a model aryl halide macrocyclic

  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。