N-Mes-azabenzonorbornadiene | 138234-31-8

• 分子结构分类: 有机化合物 - 苯类化合物 - 萘
• 英文名称: N-Mes-azabenzonorbornadiene
• 英文别名: 9-(methylsulfonyl)-1,4-dihydro-1,4-epiazano-naphthalene；7-(methylsulfonyl)-7-azabenzonorbornadiene
• CAS: 138234-31-8
• 化学式: C₁₁H₁₁NO₂S
• 分子量: 221.28
• InChiKey: RMNFWFRJXMBPOQ-PHIMTYICSA-N

物化性质

• 熔点：
  101-102 °C
• 沸点：
  368.2±52.0 °C(Predicted)
• 密度：
  1.42±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.61
• 重原子数：
  15.0
• 可旋转键数：
  1.0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.27
• 拓扑面积：
  37.38
• 氢给体数：
  0.0
• 氢受体数：
  2.0

反应信息

• 作为反应物：
  描述：

  diiron nonacarbonyl 、 N-Mes-azabenzonorbornadiene 以 四氢呋喃 为溶剂， 生成 (7-(methylsulfonyl)-7-azabenzonorbornadiene)tetracarbonyliron
  参考文献：
  名称：

  N-亲核试剂对配位羰基配体的攻击：（7-氮杂苯并降冰片二烯）四羰基铁衍生物的结构

  摘要：

  Three crystal structures of (N-substituted 7-azabenzonorbornadiene)Fe(CO)4 derivatives have been studied for substituents 7-MeSO2 (1), 7-p-CIC6H4 (2), and 7-p-MeC6H4 (3), respectively. In the solid state, an intramolecular interaction between the N-nucleophile and the nearby coordinated CO ligand is clearly seen. As the N...C = O contact distance becomes shorter, the O atom of Fe-C-O bends away from the N atom more, corresponding to a stronger interaction between the nucleophile and the coordinated CO.

  DOI：

  10.1021/om00038a074

文献信息

• Cobalt(III)-Catalyzed Intermolecular Carboamination of Propiolates and Bicyclic Alkenes via Non-Annulative Redox-Neutral Coupling
  作者：Yuelu Zhu、Feng Chen、Xinyang Zhao、Dingyuan Yan、Wanxiong Yong、Jing Zhao

  DOI：10.1021/acs.orglett.9b02016

  日期：2019.8.2

  cobalt(III)-catalyzed, redox-neutral, intermolecular carboamination of propiolates and bicyclic alkenes was developed. This non-annulative coupling strategy features atom economy, high regioselectivity, good yields, and functional groups tolerance. Such a carboamination reaction was applied to modified phenols from the corresponding phenols under mild conditions.

  开发了钴（II​​I）催化的丙酸酯和双环烯烃的氧化还原中性分子间碳氨基化反应。这种非环形的耦合策略具有原子经济，区域选择性高，产率高和官能团耐受性的特点。在温和的条件下，将这种碳氨化反应应用于来自相应酚的改性酚。
• 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。
• Cp*Rh(III)/Bicyclic Olefin Cocatalyzed C–H Bond Amidation by Intramolecular Amide Transfer
  作者：Xiaoming Wang、Tobias Gensch、Andreas Lerchen、Constantin G. Daniliuc、Frank Glorius

  DOI：10.1021/jacs.7b02725

  日期：2017.5.10

  Cp*Rh(III)-catalyzed C-H bond amidation proceeding by an intramolecular amide transfer in N-phenoxyacetamide derivatives. Combining experimental and theoretical studies, we propose that the olefin promotes a Rh(III) intermediate to undergo oxidative addition into the O-N bond to form a Rh(V) nitrenoid species and subsequently direct the nitrenoid to add to the ortho position. The amide directing group plays a dual

  在 N-苯氧基乙酰胺衍生物中通过分子内酰胺转移进行 Cp*Rh(III) 催化的 CH 键酰胺化中，发现双环烯烃作为助催化剂。结合实验和理论研究，我们提出烯烃促进 Rh(III) 中间体氧化加成到 ON 键中以形成 Rh(V) 类氮烯物质，随后引导类氮烯添加到邻位。酰胺导向基团作为可裂解的配位部分以及 CH 酰胺化的重要偶联伙伴起着双重作用。该方法在温和条件下成功应用于天然产物和上市药物的后期多样化。
• Enantioselective Hydroalkynylation of Non-Polar Carbon-Carbon Double Bonds: Iridium-Catalyzed Asymmetric Addition Reaction of Terminal Alkyne CH Bonds to Substituted Norbornadienes
  作者：Qingjing Yang、Pui Ying Choy、Baomin Fan、Fuk Yee Kwong

  DOI：10.1002/adsc.201500465

  日期：2015.7.6

  coordination, and thus poor stereo‐induction would result. The successful enantioselective hydroalkynylation of this type of system has sporadically been reported. We herein describe our progress for the example of vinyl‐substituted norbornadiene derivatives. With the aid of an iridium complex in combination with the chiral SYNPHOS ligand, the addition products could be obtained smoothly with excellent enantioselectivities

  此更新描述了对映选择性加成终端炔基的C 跨越非极性CC双键H键。立体拥挤的底物通常在这类反应中具有挑战性，因为这些烯基底物显示出较差的底物-金属中心配位，因此会导致不良的立体感应。零星地报道了这种类型系统成功的对映选择性加氢烷基化反应。在此，我们以乙烯基取代的降冰片二烯衍生物为例描述我们的进展。借助于铱配合物与手性SYNPHOS配体的结合，可以顺利获得具有优异对映选择性（最高99％ee）的加成产物。特别地，炔C的第一实施例还公开了跨氮杂降冰片二烯的H键加成。
• Rhodium(III)-Catalyzed Coupling of Arenes with 7-Oxa/Azabenzonorbornadienes by CH Activation
  作者：Zisong Qi、Xingwei Li

  DOI：10.1002/anie.201303507

  日期：2013.8.19

  Under chelation assistance, rhodium(III) complexes can catalyze the redox‐neutral coupling of arenes with 7‐oxabenzonorbornadienes and the oxidative coupling of arenes with 7‐azabenzonorbornadienes (see scheme; Cp*=C5Me5). A seven‐membered rhodacycle containing a RhC(alkyl) bond has been established as the key intermediate.

  在螯合辅助下，铑（III）络合物可以催化芳烃与7-氧杂苯并降冰片二烯的氧化还原-中性偶联，以及芳烃与7-氮杂苯并降冰片二烯的氧化偶联（见方案； Cp * = C 5 Me 5）。含有RH的七元rhodacycle  C（烷基）键已被确立为关键中间体。