Ditert-butyl 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-14,20-dicarboxylate | 1166019-20-0

• 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: Ditert-butyl 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-14,20-dicarboxylate
• CAS: 1166019-20-0
• 化学式: C₃₁H₃₃N₇O₄
• 分子量: 567.648
• InChiKey: FCMIYUYDSPOYTF-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.5
• 重原子数：
  42
• 可旋转键数：
  4
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.26
• 拓扑面积：
  133
• 氢给体数：
  2
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  Ditert-butyl 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-14,20-dicarboxylate 在 溶剂黄146 作用下， 反应 12.0h， 以82%的产率得到2,8,14,20,25,26,27-Heptazapentacyclo[19.3.1.13,7.19,13.115,19]octacosa-1(24),3(28),4,6,9,11,13,15,17,19(26),20,22-dodecaene
  参考文献：
  名称：

  Synthesis, Structure, and Reactions of NH-Bridged Calix[m]arene[n]pyridines

  摘要：

  NH-bridged calix[1]arene[3]pyridine and calix[2]arene[2]pyridine were synthesized readily from efficient deprotection of N-Boc groups of NBoc-bridged calix[m]arene[n]pyridine derivatives which were prepared by a macrocyclic coupling reaction between NBoc-linked trimers and 1,3-phenylenediamine. In the solid state, calix[2]arene[2]pyridine adopted the flattened saddle conformation, while NH-bridged calix[1]arene[3]pyridine gave a slightly twisted 1,3-alternate conformer. In both cases, all NH bridges formed partial conjugation with both pyridine and benzene rings, whereas in solution they gave symmetric conformational structures in which the conjugation of bridging NH units with pyridine ring was stronger than with benzene ring. In the presence of NaH, NH-bridged calix[2]arene[2]pyridine reacted efficiently with methyl iodide and allyl bromide to afford the corresponding N-alkylated products in almost quantitative yield. Upon treatment of NH- and NMe-bridged calix[2]arene[2]pyridines with CF3CO2D and CuBr2, deuteration and bromination reactions took place selectively on the pyridine ring, producing respectively the pyridine ring-deuterated and -brominated macrocyclic products.

  DOI：

  10.1021/jo900826n
• 作为产物：
  描述：

  tert-butyl N-(6-bromopyridin-2-yl)-N-[6-[(6-bromopyridin-2-yl)-[(2-methylpropan-2-yl)oxycarbonyl]amino]pyridin-2-yl]carbamate 、 间苯二胺 在 tris-(dibenzylideneacetone)dipalladium(0) 、 1,3-双(二苯基膦)丙烷 、 caesium carbonate 作用下， 以 1,4-二氧六环 为溶剂， 反应 24.0h， 以30%的产率得到Ditert-butyl 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-14,20-dicarboxylate
  参考文献：
  名称：

  Synthesis, Structure, and Reactions of NH-Bridged Calix[m]arene[n]pyridines

  摘要：

  NH-bridged calix[1]arene[3]pyridine and calix[2]arene[2]pyridine were synthesized readily from efficient deprotection of N-Boc groups of NBoc-bridged calix[m]arene[n]pyridine derivatives which were prepared by a macrocyclic coupling reaction between NBoc-linked trimers and 1,3-phenylenediamine. In the solid state, calix[2]arene[2]pyridine adopted the flattened saddle conformation, while NH-bridged calix[1]arene[3]pyridine gave a slightly twisted 1,3-alternate conformer. In both cases, all NH bridges formed partial conjugation with both pyridine and benzene rings, whereas in solution they gave symmetric conformational structures in which the conjugation of bridging NH units with pyridine ring was stronger than with benzene ring. In the presence of NaH, NH-bridged calix[2]arene[2]pyridine reacted efficiently with methyl iodide and allyl bromide to afford the corresponding N-alkylated products in almost quantitative yield. Upon treatment of NH- and NMe-bridged calix[2]arene[2]pyridines with CF3CO2D and CuBr2, deuteration and bromination reactions took place selectively on the pyridine ring, producing respectively the pyridine ring-deuterated and -brominated macrocyclic products.

  DOI：

  10.1021/jo900826n

文献信息

• 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。
• Designing a Cu(II)–ArCu(II)–ArCu(III)–Cu(I) Catalytic Cycle: Cu(II)-Catalyzed Oxidative Arene C–H Bond Azidation with Air as an Oxidant under Ambient Conditions
  作者：Bo Yao、Yang Liu、Liang Zhao、De-Xian Wang、Mei-Xiang Wang

  DOI：10.1021/jo502115a

  日期：2014.11.21

  On the basis of our recent discovery of high valent organocopper compounds, we have designed and achieved efficient copper(II)-catalyzed oxidative arene C-H bond azidation under very mild aerobic conditions by using NaN3 as an azide source. In the presence of a Cu(II) catalyst, a number of azacalix[1]arene[3]pyridines underwent direct arene C-H bond cupration through an electrophilic aromatic metalation

  基于我们最近对高价有机铜化合物的发现，我们通过使用NaN3作为叠氮化物源，在非常温和的需氧条件下，设计并实现了有效的铜（II）催化的氧化芳烃CH键叠氮化。在Cu（II）催化剂的存在下，许多azacalix [1] arene [3]吡啶通过亲电子芳族金属化途径直接进行芳烃CH键缩合，形成芳基铜（II）中间体。被游离铜（II）离子氧化后，将芳基铜（II）中间体转化为芳基铜（III）物种，随后将其与叠氮化物交叉偶联，从而形成芳基叠氮化物产物，并释放出铜（I）离子。在环境催化反应条件下，生成的铜（I）物质被空气氧化成铜（II），然后进入下一个催化循环。通过叠氮的简单实用的官能团转化合成功能性氮杂杯[1]芳烃[3]吡啶，证明了该方法的应用。Cu（II）-ArCu（II）-ArCu（III）-Cu（I）催化循环的展示将为设计铜（II）催化的需氧氧化芳烃CH键的活化和转化提供新的策略。
• Synthesis, Structure, and Reactions of NH-Bridged Calix[<i>m</i>]arene[<i>n</i>]pyridines
  作者：Bo Yao、De-Xian Wang、Han-Yuan Gong、Zhi-Tang Huang、Mei-Xiang Wang

  DOI：10.1021/jo900826n

  日期：2009.8.7

  NH-bridged calix[1]arene[3]pyridine and calix[2]arene[2]pyridine were synthesized readily from efficient deprotection of N-Boc groups of NBoc-bridged calix[m]arene[n]pyridine derivatives which were prepared by a macrocyclic coupling reaction between NBoc-linked trimers and 1,3-phenylenediamine. In the solid state, calix[2]arene[2]pyridine adopted the flattened saddle conformation, while NH-bridged calix[1]arene[3]pyridine gave a slightly twisted 1,3-alternate conformer. In both cases, all NH bridges formed partial conjugation with both pyridine and benzene rings, whereas in solution they gave symmetric conformational structures in which the conjugation of bridging NH units with pyridine ring was stronger than with benzene ring. In the presence of NaH, NH-bridged calix[2]arene[2]pyridine reacted efficiently with methyl iodide and allyl bromide to afford the corresponding N-alkylated products in almost quantitative yield. Upon treatment of NH- and NMe-bridged calix[2]arene[2]pyridines with CF3CO2D and CuBr2, deuteration and bromination reactions took place selectively on the pyridine ring, producing respectively the pyridine ring-deuterated and -brominated macrocyclic products.