28-Chloro-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 | 1169706-63-1

• 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-Chloro-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
• 英文别名: 28-chloro-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: 1169706-63-1
• 化学式: C₂₅H₂₄ClN₇
• 分子量: 457.965
• InChiKey: YVYAUKGYQKBAGN-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.1
• 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 potassium chloride 、 三氟甲烷磺酸亚铜(I)苯联合体 (2:1) 作用下， 以 1,4-二氧六环 、 甲醇 为溶剂， 反应 22.0h， 以65%的产率得到28-Chloro-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。
• Mechanistic Study on Cu(II)-Catalyzed Oxidative Cross-Coupling Reaction between Arenes and Boronic Acids under Aerobic Conditions
  作者：Qian Zhang、Yang Liu、Ting Wang、Xinhao Zhang、Chao Long、Yun-Dong Wu、Mei-Xiang Wang

  DOI：10.1021/jacs.8b01896

  日期：2018.4.25

  by Cu(II), transmetalation of arylboronate to ArCu(II), the redox reaction between the resulting ArCu(II)Ar' and ArCu(II) to form respectively ArCu(III)Ar' and ArCu(I), and finally reductive elimination of ArCu(III)Ar'. Under aerobic catalytic conditions, all Cu(I) ions released from reductive elimination of ArCu(III)Ar' and from protolysis of ArCu(I) were oxidized by oxygen to regenerate Cu(II) species

  近年来，现代有机铜化学受到了极大的关注，因为与贵金属相比，铜盐天然丰富、价格低廉且毒性较小。铜盐还表现出催化和介导碳-碳和碳-杂原子键形成反应的多功能性。尽管铜盐在催化中有着广泛的应用，但反应机制仍然难以捉摸。使用氮杂杯[1]芳烃[3]吡啶，一种嵌入芳烃的大环，及其分离且结构明确的ArCu(II)和ArCu(III)化合物作为分子工具，我们现在报告了一项深入的实验和计算研究以空气为氧化剂，Cu(II) 催化芳烃和硼酸之间的氧化交叉偶联反应的机理。有机铜化合物与对甲苯基硼酸的化学计量反应验证了芳基铜 (II) 而不是芳基铜 (III) 作为反应性有机金属中间体。XPS、EPR、1H NMR、HRMS 和紫外-可见光谱证据以及所有产物和铜形态的分离和量化，结合对瞬态中间体的电子结构和能量学的计算分析，提出了涉及亲电子金属化的反应序列芳烃通过 Cu(II)，芳基硼酸盐金属转移为 ArCu(II)，所得的
• 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。
• 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.