N-tert-butylbicyclo[2.2.1]hept-5-ene-endo-2,endo-3-dicarboximide | 130982-07-9

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 异吲哚及其衍生物
• 英文名称: N-tert-butylbicyclo[2.2.1]hept-5-ene-endo-2,endo-3-dicarboximide
• 英文别名: endo-N-tert-butyl-5-norbornene-2,3-dicarboxylic imide；(1R,2S,6R,7S)-4-tert-butyl-4-azatricyclo[5.2.1.02,6]dec-8-ene-3,5-dione
• CAS: 130982-07-9
• 化学式: C₁₃H₁₇NO₂
• 分子量: 219.283
• InChiKey: JYHCINVLUQHXKL-YNFQOJQRSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.3
• 重原子数：
  16
• 可旋转键数：
  1
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.69
• 拓扑面积：
  37.4
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  1-叠氮基-2-硝基苯 、 N-tert-butylbicyclo[2.2.1]hept-5-ene-endo-2,endo-3-dicarboximide 以 氯仿 为溶剂， 以95%的产率得到10-tert-butyl-5-o-nitrophenyl-3,4,5,10-tetraazatricyclo[5.5.1.0^2,6-exo.0^8,12-endo]tridec-3-ene-9,11-dione
  参考文献：
  名称：

  双环[2.2.1]庚-5-烯-2,3-二芳基酰亚胺与芳族叠氮化物的反应

  摘要：

  Reactions of N-substituted bicyclo[2.2.1]hept-5-ene-endo-2,endo-3-dicarboximides with o- and p-nitrophenyl azides, as well as with p-nitrophenylsulfonyl azide and p-toluenesulfonyl azide, afforded the corresponding substituted dihydrotriazole (from aryl azides) and arylsulfonylaziridine derivatives (from sulfonyl azides). The exo orientation of the nitrogen-containing cyclic fragments (in keeping with the Alder rule) and endo orientation of the imide ring were confirmed by analysis of the IR and H-1 and C-13 NMR spectra. The molecular structure of one of the products was examined by X-ray analysis.

  DOI：

  10.1023/b:rujo.0000045191.12939.47
• 作为产物：
  描述：

  3,6-endomethylene-1,2,3,6-tetrahydrophthalic anhydride 以 溶剂黄146 、 苯 为溶剂， 生成 N-tert-butylbicyclo[2.2.1]hept-5-ene-endo-2,endo-3-dicarboximide
  参考文献：
  名称：

  双环[2.2.1]庚-5-烯-2,3-二芳基酰亚胺与芳族叠氮化物的反应

  摘要：

  Reactions of N-substituted bicyclo[2.2.1]hept-5-ene-endo-2,endo-3-dicarboximides with o- and p-nitrophenyl azides, as well as with p-nitrophenylsulfonyl azide and p-toluenesulfonyl azide, afforded the corresponding substituted dihydrotriazole (from aryl azides) and arylsulfonylaziridine derivatives (from sulfonyl azides). The exo orientation of the nitrogen-containing cyclic fragments (in keeping with the Alder rule) and endo orientation of the imide ring were confirmed by analysis of the IR and H-1 and C-13 NMR spectra. The molecular structure of one of the products was examined by X-ray analysis.

  DOI：

  10.1023/b:rujo.0000045191.12939.47

文献信息

• Highly Active Chiral Ruthenium-Based Metathesis Catalysts through a Monosubstitution in the N-Heterocyclic Carbene
  作者：Sascha Tiede、Anke Berger、David Schlesiger、Daniel Rost、Anja Lühl、Siegfried Blechert

  DOI：10.1002/anie.201000940

  日期：2010.5.25

  Single (substitution) is better: New chiral ruthenium metathesis (pre)catalysts with a monosubstituted carbon atom in the N‐heterocyclic carbene ligand are highly stable in solution, initiate easily, show very high enantioselectivity and excellent E selectivity in asymmetric ring‐opening cross‐metathesis (see scheme).

  单（取代）更好：N-杂环卡宾配体中具有单取代碳原子的新型手性钌复分解（预）催化剂在溶液中高度稳定，易于引发，在非对称开环交叉中显示出很高的对映选择性和极好的E选择性复分解（请参阅方案）。
• A Novel Ligand for the Enantioselective Ruthenium-Catalyzed Olefin Metathesis
  作者：Axel Kannenberg、Daniel Rost、Stefan Eibauer、Sascha Tiede、Siegfried Blechert

  DOI：10.1002/anie.201007673

  日期：2011.3.28

  A bridge connects and efficiently transfers the chirality from the backbone of a N‐heterocyclic carbene (NHC) to the metal center. The result is excellent enantioselectivities in the ruthenium‐catalyzed, asymmetric ring‐opening cross‐metathesis of norbornenes with allyltrimethylsilane (see scheme).

  桥连接并有效地将手性从N杂环卡宾（NHC）的骨架传递到金属中心。结果是降冰片烯与烯丙基三甲基硅烷在钌催化的不对称开环交叉复分解中具有出色的对映选择性（参见方案）。
• Reactivity of Grubbs–Hoveyda II Complexes Including Extended N-Heterocyclic Carbenes with a Bicyclic Camphor-Based Framework
  作者：René Wilhelm、Eduard Rais、Ulrich Flörke

  DOI：10.1055/s-0036-1588849

  日期：2017.7

  Abstract This feature article discusses the synthesis of new asymmetric Grubbs–Hoveyda II complexes with extended N-heterocyclic carbenes containing a bicyclic camphor-based framework. The new enantiopure complexes can be prepared in a short route from the chiral pool. The extended carbene-based catalyst shows high activity in olefin metathesis reactions. The new complexes exhibited enantioselectivity

  摘要 这篇专题文章讨论了新的不对称Grubbs-Hoveyda II配合物的合成，该配合物具有扩展的N-杂环卡宾，其中包含基于双环樟脑的骨架。新的对映纯配合物可以在短距离内从手性池中制备。扩展的卡宾基催化剂在烯烃复分解反应中显示出高活性。新的复合物在不对称的ROCM去对称化中表现出对映选择性。根据卡宾氮原子上的取代基，过量形成相反的对映异构体。 这篇专题文章讨论了新的不对称Grubbs-Hoveyda II配合物的合成，该配合物具有扩展的N-杂环卡宾，其中包含基于双环樟脑的骨架。新的对映纯配合物可以在短距离内从手性池中制备。扩展的卡宾基催化剂在烯烃复分解反应中显示出高活性。新的复合物在不对称的ROCM去对称化中表现出对映选择性。根据卡宾氮原子上的取代基，过量形成相反的对映异构体。
• Design, Synthesis, and Self-Assembly of Polymers with Tailored Graft Distributions
  作者：Alice B. Chang、Tzu-Pin Lin、Niklas B. Thompson、Shao-Xiong Lennon Luo、Allegra L. Liberman-Martin、Hsiang-Yun Chen、Byeongdu Lee、Robert H. Grubbs

  DOI：10.1021/jacs.7b10525

  日期：2017.12.6

  polymerization (ROMP). One-pot copolymerization of an ω-norbornenyl macromonomer and a discrete norbornenyl comonomer (diluent) provides opportunities to control the backbone sequence and therefore the side chain distribution. Toward sequence control, the homopolymerization kinetics of 23 diluents were studied, representing diverse variations in the stereochemistry, anchor groups, and substituents. These

  接枝密度和接枝分布影响聚合物的链尺寸和物理性能。然而，实现对这些结构参数的精确控制提出了长期的综合挑战。在本报告中，我们介绍了一种通过接枝开环复分解聚合（ROMP）来合成具有定制结构的聚合物的通用策略。ω-降冰片烯大分子单体和离散的降冰片烯基共聚单体（稀释剂）的一锅共聚提供了控制主链序列并因此控制侧链分布的机会。为了控制序列，研究了23种稀释剂的均聚动力学，这些动力学代表了立体化学，锚定基团和取代基的各种变化。这些修饰将均聚速率常数调整到2个数量级以上（0。–1 s –1 < k homo <82 M –1 s –1）。通过互补的机理和密度泛函理论（DFT）研究确定并阐明了速率趋势。在此基础上，通过将选定的稀释剂与聚（d，l-丙交酯）（PLA），聚二甲基硅氧烷（PDMS）或聚苯乙烯（PS）大分子单体。交叉传播速率常数是根据Mayo-Lewis终端模型通过瞬时共聚单体浓度的非线性最小二乘拟合
• Consecutive Intermolecular Reductive Amination/Asymmetric Hydrogenation: Facile Access to Sterically Tunable Chiral Vicinal Diamines and N‐Heterocyclic Carbenes
  作者：Ya Chen、Yixiao Pan、Yan‐Mei He、Qing‐Hua Fan

  DOI：10.1002/anie.201909919

  日期：2019.11.18

  transformed into sterically hindered chiral N-heterocyclic carbene (NHC) precursors, which are otherwise difficult to access. The usefulness of this synthetic approach was further demonstrated by the successful application of one of the chiral vicinal diamines and chiral NHC ligands in a transition-metal-catalyzed asymmetric Suzuki-Miyaura cross-coupling reaction and asymmetric ring-opening cross-metathesis

  已经开发出具有2-喹啉醛和芳族胺的高度对映选择性的铱或钌催化的分子间还原胺化/不对称氢化继电器。以高收率（高达95％）和出色的对映选择性（高达> 99％ee）获得了范围广泛的空间可调性手性N，N'-二芳基邻位二胺。所得的手性二胺很容易转化为空间受阻的手性N-杂环卡宾（NHC）前体，否则很难获得。通过将手性邻位二胺和手性NHC配体之一分别成功应用在过渡金属催化的不对称Suzuki-Miyaura交叉偶联反应和不对称开环交叉复分解中，进一步证明了这种合成方法的有效性。