28-Iodo-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 | 1169706-66-4

• 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-Iodo-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: 1169706-66-4
• 化学式: C₂₅H₂₄IN₇
• 分子量: 549.417
• InChiKey: WMMAPGXOHUKGQZ-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-Iodo-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 potassium nitrite 、 copper(II) bis(trifluoromethanesulfonate) 作用下， 以 甲醇 为溶剂， 反应 12.0h， 以10%的产率得到2,8,14,20-Tetramethyl-28-nitro-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：

  Cu（OTf）2催化选择性Arene C–H键羟基化和硝化，其中KNO 2为邻位O和N亲核试剂，通过Cu（II）–Cu（III）–Cu（I）机理

  摘要：

  在非常温和的好氧条件下，使用KNO 2作为亲和的O-和N-亲核试剂，完成了Cu（OTf）2催化的Azacalix [1] arene [3]吡啶的选择性芳烃C–H键羟基化和硝化反应，从而生成官能化的Azacalixaromatics 。羟基化和硝化之间的选择性受所用反应介质调节的反应，是通过Cu（II）–Cu（III）–Cu（I）机理进行的。

  DOI：

  10.1021/ol401453f
• 作为产物：
  描述：

  azacalix[1]arene[3]pyridine 在 copper(II) perchlorate hexahydrate 、 potassium iodide 作用下， 以 甲醇 、 氯仿 、 乙腈 为溶剂， 反应 3.5h， 生成 28-Iodo-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：

  Cu（ClO 4）2介导的碱金属卤化物为氮杂芳烃的芳烃CH键卤代反应

  摘要：

  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。

  DOI：

  10.1021/jo300152u

文献信息

• Construction of C_aryl–C_alkynyl Bond from Copper-Mediated Arene–Alkyne and Aryl Iodide–Alkyne Cross-Coupling Reactions: A Common Aryl-Cu^III Intermediate in Arene C–H Activation and Castro–Stephens Reaction
  作者：Zu-Li Wang、Liang Zhao、Mei-Xiang Wang

  DOI：10.1021/ol300205r

  日期：2012.3.16

  Both copper(II)-mediated oxidative C–H bond activation and oxidative addition of copper(I) into a C–I bond produced an identical and structurally well-defined aryl-Cu(III) intermediate. The cross-coupling reaction of an aryl-Cu(III) intermediate with both terminal alkynes at an elevated temperature and alkynyllithium reagents under mild conditions led effectively to the formation of a Caryl–Calkynyl

  铜（II）介导的氧化性C–H键活化和铜（I）的氧化加成至C–I键均产生相同且结构明确的芳基-Cu（III）中间体。在高温下，芳基-Cu（III）中间体与两个末端炔烃和温和条件下的炔基锂试剂的交叉偶联反应有效地导致了C芳基-C炔基键的形成。已经为卡斯特罗-斯蒂芬斯反应提出了另一种机制。
• 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。
• 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.