N-benzoyl-7-azabenzobicyclo[2.2.1]heptadiene | 34353-23-6

• 分子结构分类: 有机化合物 - 苯类化合物 - 萘
• 英文名称: N-benzoyl-7-azabenzobicyclo[2.2.1]heptadiene
• 英文别名: 11-Azatricyclo[6.2.1.02,7]undeca-2,4,6,9-tetraen-11-yl(phenyl)methanone
• CAS: 34353-23-6
• 化学式: C₁₇H₁₃NO
• 分子量: 247.296
• InChiKey: JZQBWFCQNSFHHK-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.1
• 重原子数：
  19
• 可旋转键数：
  1
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.12
• 拓扑面积：
  20.3
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  N-benzoyl-7-azabenzobicyclo[2.2.1]heptadiene 在 钌 作用下， 以 苯 为溶剂， 反应 4.0h， 生成 dimethyl (1R,8S,9S,10S,12R,13R)-14-benzoyl-11-benzyl-11,14-diazapentacyclo[6.5.1.02,7.09,13.010,12]tetradeca-2,4,6-triene-10,12-dicarboxylate
  参考文献：
  名称：

  Inside and outside N-bridged cavity systems: evidence for syn- and anti-atropisomers in scaffolds containing two N-benzoyl 7-azanorbornane units

  摘要：

  Alkene and aziridine reagents containing N-benzoyl 7-azanorbornane components have been prepared and used to construct [n]polynorbornanes in a block building protocol. The presence of syn- and anti-atropisomers involving the restricted rotation of the N-COPh bridge was established by H-1 NMR spectroscopy in an NNN-[3]polynorbornane 4 (outside bridges) whereas the anti-conformer dominated in a cavity NCOCOCN-[7]isopolynorbornane 8 (inside bridges, X-ray confirmation) prepared by a dual 1,3-dipolar addition of an acute-angled norbornene 6 with a hexacyclic bis-epoxide 7. (C) 2001 Published by Elsevier Science Ltd.

  DOI：

  10.1016/s0040-4039(00)01939-0
• 作为产物：
  描述：

  邻溴氟苯 在 palladium on activated charcoal 氢气 、 magnesium 、 三乙胺 、 三氟乙酸 作用下， 以 四氢呋喃 、 甲醇 、 二氯甲烷 为溶剂， 反应 14.0h， 生成 N-benzoyl-7-azabenzobicyclo[2.2.1]heptadiene
  参考文献：
  名称：

  7-氮杂双环[2.2.1]庚烷酰胺中酰胺基团平面性的评价。溶液中的低酰胺键旋转屏障

  摘要：

  在这里，我们表明双环 7-氮杂双环 [2.2.1] 庚烷的酰胺本质上是氮锥体。一些相关双环酰胺的单晶 X 射线衍射结构，包括原型 N-苯甲酰基-7-氮杂双环 [2.2.1] 庚烷，在固态下表现出氮锥体化。我们评估了溶液中各种 N-苯甲酰基-7-氮杂双环 [2.2.1] 庚烷的酰胺键的旋转势垒。与单环吡咯烷酰胺相比，观察到的双环酰胺旋转势垒的降低与溶液中 7-氮杂双环 [2.2.1] 庚烷酰胺的氮-锥体结构一致。发现在苯甲酰基上带有对位取代基的 N-苯甲酰基-7-氮杂双环[2.2.1]庚烷的旋转势垒的大小与哈米特'之间存在良好的相关性 s sigma(p)(+) 常数，这与解结构的相似性一致。使用密度泛函理论的计算再现了这些双环酰胺的氮-锥体结构作为能量最小值。通过应用键模型理论评估的从氮非键合 n(N) 轨道到酰胺基团的羰基 pi 轨道计算的电子离域量与各种酰胺的旋转势垒很好地相关，包括 7-氮杂双环的酰胺[2

  DOI：

  10.1021/ja036644z

文献信息

• Palladium/Copper Complexes Co-Catalyzed Highly Enantioselective Ring Opening Reaction of Azabenzonorbornadienes with Terminal Alkynes
  作者：Baomin Fan、Sifeng Li、Hualei Chen、Zhiwu Lu、Shanshan Liu、Qingjing Yang、Lu Yu、Jianbin Xu、Yongyun Zhou、Jun Wang

  DOI：10.1002/adsc.201300748

  日期：2013.10.11

  AbstractA chiral palladium/copper (Pd/Cu) co‐catalytic system which could enable asymmetric ring opening reaction of azabenzonorbornadienes with terminal alkynes is reported. This system comprises palladium(II) acetate [Pd(OAc)2]/(R)‐xyl‐Binap and copper(I) triflate (CuOTf). A good substrate scope was found, with excellent enantioselective outcomes (up to >99.9 % ee). A reaction mechanism involving two metal complexes is also proposed.magnified image
• Enantioselective Palladium-Catalyzed Ring-Opening Reaction of Azabenzonorbornadienes with Methyl 2-Iodobenzoate: An Efficient Access to<i>cis</i>-Dihydrobenzo[<i>c</i>]phenanthridinones
  作者：Kang-Lun Huang、Cui Guo、Li-Jie Cheng、Long-Guan Xie、Qi-Lin Zhou、Xiao-Hua Xu、Shou-Fei Zhu

  DOI：10.1002/adsc.201300452

  日期：2013.10.11

  AbstractThe palladium‐catalyzed asymmetric ring‐opening (ARO) reaction of azabenzonorbornadienes with iodobenzoate derivatives was realized by using chiral spirophosphine ligands with zinc powder as a reducing reagent. Various enantiomerically enriched cis‐dihydrobenzo[c]phenanthridinones, the core structure of numerous chiral natural products, were prepared by the ARO reaction and tandem amidation from easily obtained starting materials with favorable enantioselectivity (up to 86% ee) under mild reaction conditions. The present palladium‐catalyzed ARO reaction avoids the direct use of organometallic reagents, enables tandem cyclization, and thus improves synthetic efficiency. The formal total synthesis of a chiral natural product, (+)‐chelidonine, was accomplished with the ARO reaction as a key step, which demonstrates the potential synthetic applications of the present methodology.magnified image
• An Evaluation of Amide Group Planarity in 7-Azabicyclo[2.2.1]heptane Amides. Low Amide Bond Rotation Barrier in Solution
  作者：Yuko Otani、Osamu Nagae、Yuji Naruse、Satoshi Inagaki、Masashi Ohno、Kentaro Yamaguchi、Gaku Yamamoto、Masanobu Uchiyama、Tomohiko Ohwada

  DOI：10.1021/ja036644z

  日期：2003.12.1

  Single-crystal X-ray diffraction structures of some relevant bicyclic amides, including the prototype N-benzoyl-7-azabicyclo[2.2.1]heptane, exhibited nitrogen-pyramidalization in the solid state. We evaluated the rotational barriers about the amide bonds of various N-benzoyl-7-azabicyclo[2.2.1]heptanes in solution. The observed reduction of the rotational barriers of the bicyclic amides, as compared with

  在这里，我们表明双环 7-氮杂双环 [2.2.1] 庚烷的酰胺本质上是氮锥体。一些相关双环酰胺的单晶 X 射线衍射结构，包括原型 N-苯甲酰基-7-氮杂双环 [2.2.1] 庚烷，在固态下表现出氮锥体化。我们评估了溶液中各种 N-苯甲酰基-7-氮杂双环 [2.2.1] 庚烷的酰胺键的旋转势垒。与单环吡咯烷酰胺相比，观察到的双环酰胺旋转势垒的降低与溶液中 7-氮杂双环 [2.2.1] 庚烷酰胺的氮-锥体结构一致。发现在苯甲酰基上带有对位取代基的 N-苯甲酰基-7-氮杂双环[2.2.1]庚烷的旋转势垒的大小与哈米特'之间存在良好的相关性 s sigma(p)(+) 常数，这与解结构的相似性一致。使用密度泛函理论的计算再现了这些双环酰胺的氮-锥体结构作为能量最小值。通过应用键模型理论评估的从氮非键合 n(N) 轨道到酰胺基团的羰基 pi 轨道计算的电子离域量与各种酰胺的旋转势垒很好地相关，包括 7-氮杂双环的酰胺[2
• Inside and outside N-bridged cavity systems: evidence for syn- and anti-atropisomers in scaffolds containing two N-benzoyl 7-azanorbornane units
  作者：Ronald N Warrener、Guangxing Sun

  DOI：10.1016/s0040-4039(00)01939-0

  日期：2001.1

  Alkene and aziridine reagents containing N-benzoyl 7-azanorbornane components have been prepared and used to construct [n]polynorbornanes in a block building protocol. The presence of syn- and anti-atropisomers involving the restricted rotation of the N-COPh bridge was established by H-1 NMR spectroscopy in an NNN-[3]polynorbornane 4 (outside bridges) whereas the anti-conformer dominated in a cavity NCOCOCN-[7]isopolynorbornane 8 (inside bridges, X-ray confirmation) prepared by a dual 1,3-dipolar addition of an acute-angled norbornene 6 with a hexacyclic bis-epoxide 7. (C) 2001 Published by Elsevier Science Ltd.