1,4-dihydro-1,4-epiazano-6,7-dimethylnaphthalene-9-carbamic acid tert-butyl ester

• 分子结构分类: 有机化合物 - 苯类化合物 - 萘
• 英文名称: 1,4-dihydro-1,4-epiazano-6,7-dimethylnaphthalene-9-carbamic acid tert-butyl ester
• 英文别名: tert-butyl 6,7-dimethyl-1,4-dihydro-1,4-epiminonaphthalene-9-carboxylate；tert-butyl (1S,8R)-4,5-dimethyl-11-azatricyclo[6.2.1.02,7]undeca-2(7),3,5,9-tetraene-11-carboxylate
• 化学式: C₁₇H₂₁NO₂
• 分子量: 271.359
• InChiKey: CEEREWWTLCHPCF-GASCZTMLSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.5
• 重原子数：
  20
• 可旋转键数：
  2
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.47
• 拓扑面积：
  29.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  1,4-dihydro-1,4-epiazano-6,7-dimethylnaphthalene-9-carbamic acid tert-butyl ester 在 水 、 palladium diacetate 、 zinc trifluoromethanesulfonate 、 (S)-(-)-5,5-双(二苯膦基)-4,4-双-1,3-苯并间二氧杂环戊烯 、 锌 作用下， 以 1,4-二氧六环 为溶剂， 反应 7.0h， 以95%的产率得到(S)-tert-butyl (6,7-dimethyl-1,2-dihydronaphthalen-1-yl)carbamate
  参考文献：
  名称：

  以水为氢源的杂环双烯烃不对称转移加氢

  摘要：

  杂双环烯烃的不对称转移氢化是通过使用水作为唯一的氢源来完成的。Pd（OAc）2 / Zn（OTf）2双重催化剂与金属锌作为还原剂共同催化转化。通过不对称的还原性开环反应，各种氮杂苯并降冰片二烯和氧杂苯并降冰片二烯被转化为相应的手性1,2-二氢萘，具有良好的至优异的对映选择性。

  DOI：

  10.1021/acs.orglett.9b00059
• 作为产物：
  描述：

  邻二甲苯 在 正丁基锂 、 溴 、 碘 作用下， 以 甲苯 为溶剂， 反应 16.0h， 生成 1,4-dihydro-1,4-epiazano-6,7-dimethylnaphthalene-9-carbamic acid tert-butyl ester
  参考文献：
  名称：

  Synthesis of Cyclopropanated 7-Azabenzonorbornadienes

  摘要：

  7-Azabenzonorbornadienes bearing various aryl or N-substituents were treated with diazomethane in the presence of palladium to afford desirable yields of cyclopropanated products (75-98%). The current approach suggests an efficient synthesis for CH2-cyclopropanated 7-azabenzonorbornadienes which lends promise to the development of new ring-opening preparations of biologically useful organic frameworks.

  DOI：

  10.1055/s-0035-1561600

文献信息

• Palladium/Lewis Acid Cocatalyzed Reductive Asymmetric Ring-Opening Reaction of Azabenzonorbornadienes with Tertiary Amines as the Hydrogen Source
  作者：Dapeng Zhang、Ruhima Khan、Fan Yang、Xuexin Zhang、Guoli Shen、Yang Gao、Ruifeng Fan、Weiqing Sun、Baomin Fan

  DOI：10.1002/ejoc.201800503

  日期：2018.7.13

  Palladium and silver cocatalyzed the asymmetric transfer hydrogenation of azabenzonorbornadienes with tertiary amines to give the corresponding ring‐opening products in high yields with good to excellent enantioselectivities. (R)‐2,2′‐Bis(diphenylphosphino)‐1,1′‐binaphthyl [(R)‐BINAP] and para‐methoxybenzoic acid were used as the chiral ligand and additive, respectively, in the reported protocol.

  钯和银共催化氮杂苯并降冰片二烯与叔胺的不对称转移加氢，从而以高收率和良好或优异的对映选择性提供相应的开环产物。（R）-2,2'-双（二苯基膦基）-1,1'-联萘[[ R）-BINAP]和对-甲氧基苯甲酸分别用作所报告的方案中的手性配体和添加剂。
• Palladium/Lewis Acid Co-catalyzed Divergent Asymmetric Ring-Opening Reactions of Azabenzonorbornadienes with Alcohols
  作者：Fan Yang、Jingchao Chen、Jianbin Xu、Fujie Ma、Yongyun Zhou、Madhuri Vikas Shinde、Baomin Fan

  DOI：10.1021/acs.orglett.6b02300

  日期：2016.10.7

  catalysts and Lewis acids, both the additional and reductive asymmetric ring-opening reactions of azabenzonorbornadienes with alcohols were accomplished with good chemoselectivity, regioselectivity, and enantioselectivity. It was proven that the reductive ring-opening products were generated through a transfer-hydrogenation process with alcohols as hydrogen source.

  通过微调手性钯催化剂和路易斯酸的组合，氮杂苯并降冰片二烯与醇的附加和还原性不对称开环反应均具有良好的化学选择性，区域选择性和对映选择性。事实证明，还原性开环产物是通过以醇为氢源的转移加氢过程产生的。
• A Readily Accessible Class of Chiral Cp Ligands and their Application in Ru ^II ‐Catalyzed Enantioselective Syntheses of Dihydrobenzoindoles
  作者：Shou‐Guo Wang、Sung Hwan Park、Nicolai Cramer

  DOI：10.1002/anie.201802244

  日期：2018.5.4

  Chiral cyclopentadienyl (Cpx) ligands have a large application potential in enantioselective transition‐metal catalysis. However, the development of concise and practical routes to such ligands remains in its infancy. We present a convenient and efficient two‐step synthesis of a novel class of chiral Cpx ligands with tunable steric properties that can be readily used for complexation, giving CpxRhI

  手性环戊二烯（Cp x）配体在对映选择性过渡金属催化中具有巨大的应用潜力。但是，开发这种配体的简洁实用的方法仍处于起步阶段。我们提出了一种方便有效的两步合成具有可调空间特性的新型手性Cp x配体的方法，可以很容易地用于络合，得到Cp x Rh I，Cp x Ir I和Cp x Ru II复合体。后者在用炔烃对氮杂苯并降冰片二烯进行对映选择性环化中得到了证明，后者可提供高达98：2 er的二氢苯并吲哚，显着优于现有的由双萘基衍生的Cp x配体。
• Directing-Group-Controlled Ring-Opening Addition and Hydroarylation of Oxa/azabenzonorbornadienes with Arenes via C–H Activation
  作者：Keyang Zhang、Ruhima Khan、Jingchao Chen、Xuexin Zhang、Yang Gao、Yongyun Zhou、Kangkui Li、Youxian Tian、Baomin Fan

  DOI：10.1021/acs.orglett.0c00765

  日期：2020.5.1

  rhodium-catalyzed addition reaction of oxa/azabicylic alkenes with aromatic ketones and benzoic acids has been developed. The ketones and benzoic acids afforded different addition products when reacted with oxa/azabicyclic alkenes. The reaction between ketones and azabenzonorbornadienes furnished the ring-opening addition products. The reaction between benzoic acids and aza/oxabicyclic alkenes proceeded in

  已开发出一种有效的方法来指导基团控制的铑催化的氧杂/氮杂双环烯烃与芳族酮和苯甲酸的加成反应。当与氧杂/氮杂双环烯烃反应时，酮和苯甲酸提供不同的加成产物。酮与氮杂苯并降冰片二烯之间的反应提供了开环加成产物。苯甲酸和氮杂/氧杂双环烯烃之间的反应在不存在银盐的情况下进行，得到1：2的氢芳基化产物，收率高达96％。
• Combination of Cp*Rh ^III ‐Catalyzed C−H Activation and a Wagner–Meerwein‐Type Rearrangement
  作者：Xiaoming Wang、Andreas Lerchen、Tobias Gensch、Tobias Knecht、Constantin G. Daniliuc、Frank Glorius

  DOI：10.1002/anie.201610117

  日期：2017.1.24

  A combination of Cp*RhIII‐catalyzed C−H activation and Wagner–Meerwein‐type rearrangement was successfully achieved for the first time. Thus, bridged polycyclic molecules that are not readily accessible by other means were accessed under mild conditions with high efficiency (as low as 0.5 mol % Rh catalyst) in the coupling of N‐phenoxyacetamide with 7‐azabenzonorbornadiene.

  首次成功实现了Cp * Rh III催化的CH活化和Wagner-Meerwein型重排的结合。因此，在N-苯氧基乙酰胺与7-氮杂苯并降冰片二烯的偶联反应中，在温和的条件下以高效率（低至0.5 mol％Rh催化剂）可以容易地通过其他途径难以接近的桥联多环分子被接近。