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-ol | 1169706-64-2

• 分子结构分类: 有机化合物 - 苯类化合物 - 酚类
• 英文名称: 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-ol
• 英文别名: 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-ol
• CAS: 1169706-64-2
• 化学式: C₂₅H₂₅N₇O
• 分子量: 439.52
• InChiKey: XULLMRUYMFQPGV-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.2
• 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：
  78.6
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为反应物：
  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-ol 在 4-二甲氨基吡啶 、 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 、 二氯甲烷 为溶剂， 反应 40.0h， 生成 Methyl 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-28-carboxylate
  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
• 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 sodium thiophenolate 、 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 、 水 为溶剂， 反应 6.0h， 以75%的产率得到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-ol
  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(OTf)₂-Catalyzed Selective Arene C–H Bond Hydroxylation and Nitration with KNO₂ as an Ambident <i>O</i>- and <i>N</i>-Nucleophile via a Cu(II)–Cu(III)–Cu(I) Mechanism
  作者：Hu Zhang、Liang Zhao、De-Xian Wang、Mei-Xiang Wang

  DOI：10.1021/ol401453f

  日期：2013.8.2

  Cu(OTf)2-catalyzed selective arene C–H bond hydroxylation and nitration reactions of azacalix[1]arene[3]pyridines were achieved using KNO2 as an ambident O- and N-nucleophile under very mild aerobic conditions to yield functionalized azacalixaromatics. The reaction, which selectivity between hydroxylation and nitration was modulated by the reaction medium employed, proceeded through a Cu(II)–Cu(III)–Cu(I) mechanism

  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。
• 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.