28-Bromo-2,8,14,20-tetramethyl-2,8,14,20,25,26,27-heptazapentacyclo[19.3.1.13,7.19,13.115,19]octacosa-1(25),3(28),4,6,9(27),10,12,15,17,19(26),21,23-dodecaene | 1169706-65-3

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡啶及其衍生物
• 英文名称: 28-Bromo-2,8,14,20-tetramethyl-2,8,14,20,25,26,27-heptazapentacyclo[19.3.1.13,7.19,13.115,19]octacosa-1(25),3(28),4,6,9(27),10,12,15,17,19(26),21,23-dodecaene
• CAS: 1169706-65-3
• 化学式: C₂₅H₂₄BrN₇
• 分子量: 502.416
• InChiKey: DTLIJEPXWPZXKD-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.2
• 重原子数：
  33
• 可旋转键数：
  0
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.16
• 拓扑面积：
  58.4
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  28-Bromo-2,8,14,20-tetramethyl-2,8,14,20,25,26,27-heptazapentacyclo[19.3.1.13,7.19,13.115,19]octacosa-1(25),3(28),4,6,9(27),10,12,15,17,19(26),21,23-dodecaene 在 正丁基锂 、 重水 作用下， 以 四氢呋喃 为溶剂， 反应 0.5h， 以95%的产率得到
  参考文献：
  名称：

  高价芳基-Cu(II) 和芳基-Cu(III) 化合物的直接合成：对芳烃 C-H 键金属化的机理洞察

  摘要：

  铜及其盐储量丰富、价格低廉且对环境友好，已被用作贵金属的替代物来影响芳烃 CH 键的活化和转化。尽管最近该研究取得了重大进展，但高价芳基铜 (II-III) 化合物的合成仍然非常罕见，铜 (II) 催化反应的机制仍然难以捉摸。使用氮杂杯[1]芳烃[3]吡啶作为平台，在环境条件下由Cu(ClO4)2反应有效地合成了许多芳基铜(II)化合物。得到的芳基-Cu(II) 化合物含有前所未有的（取代的）苯基-Cu(II) σ-键，在大气条件下稳定，并且可以通过游离铜 (II) 离子或氧酮进行容易的氧化反应，得到芳基铜(III) 收率良好的化合物。芳基铜 (II) 和芳基铜 (III) 化合物均通过 XRD、XPS 和 NMR 方法明确表征。包括反应动力学、LFER 和 KIE 在内的实验证据以及理论计算表明，Cu(ClO4)2 介导的芳烃 CH 键活化似乎是通过亲电芳香族金属化途径进行的。这里报道的

  DOI：

  10.1021/ja412615h
• 作为产物：
  描述：

  (2,8,14,20-Tetramethyl-2,8,14,20,25,26,27-heptazapentacyclo[19.3.1.13,7.19,13.115,19]octacosa-1(25),3(28),4,6,9(27),10,12,15,17,19(26),21,23-dodecaen-28-yl) trifluoromethanesulfonate 在 三氟甲烷磺酸亚铜(I)苯联合体 (2:1) 、 potassium bromide 作用下， 以 1,4-二氧六环 、 甲醇 为溶剂， 反应 13.0h， 以65%的产率得到28-Bromo-2,8,14,20-tetramethyl-2,8,14,20,25,26,27-heptazapentacyclo[19.3.1.13,7.19,13.115,19]octacosa-1(25),3(28),4,6,9(27),10,12,15,17,19(26),21,23-dodecaene
  参考文献：
  名称：

  Copper(I)-Catalyzed Halogenation and Acyloxylation of Aryl Triflates through a Copper(I)/Copper(III) Catalytic Cycle

  摘要：

  Catalyzed by CuOTf under very mild conditions, aryl triflates which are embedded in the azacalix[1]-arene[3]pyridine macrocycle underwent coupling reactions with metal halides and acetates to afford respectively halogenated and acyloxylated arene products in moderate to excellent yields. The unprecedented CuOTf-catalyzed transformations of aryl triflates proceeded through an oxidative addition of intramolecularly chelated Cu(I) into the C-O bond of aryl triflates to form arylcopper(III) intermediates which underwent anion exchange and reductive elimination reactions with nucleophiles to yield functionalized macrocyclic products.

  DOI：

  10.1021/om500046g

文献信息

• Room-temperature aerobic formation of a stable aryl–Cu(iii) complex and its reactions with nucleophiles: highly efficient and diverse arene C–H functionalizations of azacalix[1]arene[3]pyridine
  作者：Bo Yao、De-Xian Wang、Zhi-Tang Huang、Mei-Xiang Wang

  DOI：10.1039/b902946j

  日期：——

  Under very mild aerobic conditions, azacalix[1]arene[3]pyridine underwent highly efficient C-H activation with Cu(ClO(4))(2).6H(2)O to form a stable aryl-Cu(III) complex which reacted rapidly with various nucleophiles at ambient temperature to afford diverse functionalized azacalix[1]arene[3]pyridine derivatives in excellent yields.

  在非常温和的好氧条件下，azacalix [1] arene [3]吡啶经过高效的CH活化，与Cu（ClO（4））（2）.6H（2）O形成稳定的芳基-Cu（III）复合物在室温下与各种亲核试剂迅速结合，以优异的收率提供各种功能化的氮杂杯[1]亚芳基[3]吡啶衍生物。
• Cu(ClO₄)₂-Mediated Arene C–H Bond Halogenations of Azacalixaromatics Using Alkali Metal Halides as Halogen Sources
  作者：Bo Yao、Zu-Li Wang、Hu Zhang、De-Xian Wang、Liang Zhao、Mei-Xiang Wang

  DOI：10.1021/jo300152u

  日期：2012.4.6

  Regiospecific halogenation of azacalix[1]arene[3]pyridines at the lower rim position of the benzene ring was achieved from their cross-coupling reaction with cost-effective alkali metal halides through the Cu(ClO4)2-mediated aerobic aryl C–H activation, which gave structurally well-defined aryl-Cu(III) intermediates, and a subsequent C–X bond formation reaction under very mild conditions.

  氮杂杯[1]芳烃[3]吡啶在苯环较低边缘位置的区域特异性卤化反应是通过它们与具成本效益的碱金属卤化物通过Cu（ClO 4）2介导的好氧芳基C–的交叉偶联反应实现的。H活化，产生结构上明确的芳基-Cu（III）中间体，随后在非常温和的条件下形成C-X键。
• Macrocyclic Aryl–Nickel(II) Complexes: Synthesis, Structure, and Reactivity Studies
  作者：Chi Yang、Wen-Di Wu、Liang Zhao、Mei-Xiang Wang

  DOI：10.1021/acs.organomet.5b00733

  日期：2015.10.26

  The synthesis, characterization, and reactivity of the monoaryl-Ni(II) compound 2 and the diaryl-Ni(II) compound 4 formed through the direct electrophilic metalation of two macrocydic azacalix[m]arene[n]pyridine ligands are described. Compound 4 was much more stable in protic solvents and acids than the monoaryl-Ni(II) compound 2. Moreover, 2 can react with a variety of nucleophiles, resulting in the formation of C-C, C-O, C-Br, and C-N bonds. In contrast, compound 4 exhibited very inert reactivity upon reaction with a large numberof nudeophiles. Interestingly, compound 2 was also capable of reacting with several less bulky alkyl halides to form new C-C bonds, while the same procedure is inapplicable to 4. The study reported in this work provides a thorough investigation on the reactivity of aryl-Ni(II) species that should facilitate comprehension of the detailed mechanism of nickel-catalyzed C-H functionalization.
• Copper(I)-Catalyzed Halogenation and Acyloxylation of Aryl Triflates through a Copper(I)/Copper(III) Catalytic Cycle
  作者：Chao Long、Liang Zhao、Jing-Song You、Mei-Xiang Wang

  DOI：10.1021/om500046g

  日期：2014.2.24

  Catalyzed by CuOTf under very mild conditions, aryl triflates which are embedded in the azacalix[1]-arene[3]pyridine macrocycle underwent coupling reactions with metal halides and acetates to afford respectively halogenated and acyloxylated arene products in moderate to excellent yields. The unprecedented CuOTf-catalyzed transformations of aryl triflates proceeded through an oxidative addition of intramolecularly chelated Cu(I) into the C-O bond of aryl triflates to form arylcopper(III) intermediates which underwent anion exchange and reductive elimination reactions with nucleophiles to yield functionalized macrocyclic products.
• Direct Synthesis of High-Valent Aryl–Cu(II) and Aryl–Cu(III) Compounds: Mechanistic Insight into Arene C–H Bond Metalation
  作者：Hu Zhang、Bo Yao、Liang Zhao、De-Xian Wang、Bo-Qing Xu、Mei-Xiang Wang

  DOI：10.1021/ja412615h

  日期：2014.4.30

  Copper and its salts are abundant, inexpensive, and eco-friendly and have been used as the surrogates of noble metals to effect arene C-H bond activation and transformations. Despite of the recent significant progress of the study, syntheses of high-valent arylcopper(II-III) compounds are still very rare and mechanisms of copper(II)-catalyzed reactions remain elusive. With the use of azacalix[1]arene[3]pyridines

  铜及其盐储量丰富、价格低廉且对环境友好，已被用作贵金属的替代物来影响芳烃 CH 键的活化和转化。尽管最近该研究取得了重大进展，但高价芳基铜 (II-III) 化合物的合成仍然非常罕见，铜 (II) 催化反应的机制仍然难以捉摸。使用氮杂杯[1]芳烃[3]吡啶作为平台，在环境条件下由Cu(ClO4)2反应有效地合成了许多芳基铜(II)化合物。得到的芳基-Cu(II) 化合物含有前所未有的（取代的）苯基-Cu(II) σ-键，在大气条件下稳定，并且可以通过游离铜 (II) 离子或氧酮进行容易的氧化反应，得到芳基铜(III) 收率良好的化合物。芳基铜 (II) 和芳基铜 (III) 化合物均通过 XRD、XPS 和 NMR 方法明确表征。包括反应动力学、LFER 和 KIE 在内的实验证据以及理论计算表明，Cu(ClO4)2 介导的芳烃 CH 键活化似乎是通过亲电芳香族金属化途径进行的。这里报道的