endo-2-nitro-exo-3-phenylbicyclo<2.2.1>hept-5-ene | 17197-96-5

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: endo-2-nitro-exo-3-phenylbicyclo<2.2.1>hept-5-ene
• 英文别名: endo-5-nitro-exo-6-phenylbicyclo<2.2.1>hept-2-ene；nitro-2 phenyl-3 bicyclo<2,2,1>heptene-5；5-nitro-6-phenylbicyclo[2.2.1]hept-2-ene；5-endo-nitro-6-exo-phenylnorbornene；6-exo-phenyl-5-endo-nitrobenzene；(+/-)-3endo-nitro-2exo-phenyl-norbornene-(5)；(1R,4S,5R,6S)-5-nitro-6-phenylbicyclo[2.2.1]hept-2-ene
• CAS: 17197-96-5；17197-97-6；92028-79-0；96191-71-8；96191-72-9；112711-47-4
• 化学式: C₁₃H₁₃NO₂
• 分子量: 215.252
• InChiKey: ABLIRAIUNBLRPK-UMSGYPCISA-N

物化性质

• 沸点：
  124 °C(Press: 0.5 Torr)
• 密度：
  1.22±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.7
• 重原子数：
  16
• 可旋转键数：
  1
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.38
• 拓扑面积：
  45.8
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  endo-2-nitro-exo-3-phenylbicyclo<2.2.1>hept-5-ene 在 2-benzylaminopyridinium substituted-borate salt 作用下， 以 氘代甲苯 为溶剂， 反应 8.0h， 生成
  参考文献：
  名称：

  2-Aminopyridinium Ions Activate Nitroalkenes through Hydrogen Bonding

  摘要：

  2-Aminopyridinium ions were found to activate nitroalkenes toward conjugate addition of heteroaromatic compounds with low catalyst loadings and the Diels-Alder reaction with the periselectivity opposite to that observed with metal Lewis acids, raising the possibility that a 2-aminopyridinium core might be a promising catalaphore for the asymmetric catalyst design.

  DOI：

  10.1021/ol071032v
• 作为产物：
  描述：

  在 2-benzylaminopyridinium substituted-borate salt 作用下， 以 氘代甲苯 为溶剂， 反应 8.0h， 生成 endo-2-nitro-exo-3-phenylbicyclo<2.2.1>hept-5-ene
  参考文献：
  名称：

  2-Aminopyridinium Ions Activate Nitroalkenes through Hydrogen Bonding

  摘要：

  2-Aminopyridinium ions were found to activate nitroalkenes toward conjugate addition of heteroaromatic compounds with low catalyst loadings and the Diels-Alder reaction with the periselectivity opposite to that observed with metal Lewis acids, raising the possibility that a 2-aminopyridinium core might be a promising catalaphore for the asymmetric catalyst design.

  DOI：

  10.1021/ol071032v

文献信息

• Activation of Alcohols with Carbon Dioxide: Intermolecular Allylation of Weakly Acidic Pronucleophiles
  作者：Simon B. Lang、Theresa M. Locascio、Jon A. Tunge

  DOI：10.1021/ol502023d

  日期：2014.8.15

  coupling of allyl alcohols with nitroalkanes, nitriles, and aldehydes using catalytic Pd(PPh3)4 has been accomplished via activation of C–OH bonds with CO2. The in situ formation of carbonates from alcohols and CO2 facilitates oxidative addition to Pd to form reactive π-allylpalladium intermediates. In addition, the formation of a strong base activates nucleophiles toward the reaction with the π-allylpalladium

  使用催化 Pd(PPh 3 ) 4的烯丙醇与硝基烷烃、腈和醛的直接偶联是通过用 CO 2活化 C-OH 键来实现的。由醇和CO 2原位形成碳酸盐有利于Pd的氧化加成，形成反应性π-烯丙基钯中间体。此外，强碱的形成会激活亲核试剂与 π-烯丙基钯亲电子试剂发生反应。总体而言，这种原子经济反应无需使用外部碱即可提供新的 C-C 键，并生成水作为唯一的副产物。
• Electrophilic addition to norbornene derivatives containing CF3 and NO2 groups
  作者：N. V. Zyk、E. K. Beloglazkina、S. E. Sosonyuk、M. N. Bulanov、R. L. Antipin

  DOI：10.1007/s11172-005-0432-z

  日期：2005.6

  of bicyclo[2.2.1]heptenes containing CF3 or NO2 group in position endo-5 were studied. The sulfenylation and selenenation were accomplished by arylsulfene- and arylselenenamides activated by POHal3 (Hal = Br, Cl), and iodination was performed by KICl2. The reactions are regiospecific and involve an exo-attack of the electrophilic fragment (arylthio or arylseleno group or iodine) on the C=C bond atom

  研究了在endo-5 位置含有CF3 或NO2 基团的双环[2.2.1] 庚烯的亲电亚磺酰化、硒化和卤化。亚磺酰化和硒化是通过 POHal3 (Hal = Br, Cl) 激活的芳基亚砜和芳基硒酰胺完成的，碘化是通过 KICl2 进行的。这些反应是区域特异性的，涉及亲电片段（芳硫基或芳基硒基或碘）对位于更靠近 CF3 或 NO2 基团的 C=C 键原子的外向攻击。
• Stereoselectivity and kinetics of [4 + 2] cycloaddition reaction of cyclopentadiene to para-substituted E-2-arylnitroethenes
  作者：Radomir Jasiński、Magdalena Kwiatkowska、Andrzej Barański

  DOI：10.1002/poc.1853

  日期：——

  E‐2‐arylnitroethenes, their [4 + 2] cycloaddition reactions with cyclopentadiene leads to the corresponding 6‐endo‐aryl‐5‐exo‐nitronorbornenes and 6‐exo‐aryl‐5‐endo‐nitronorbornenes as the only reaction products. Stereoselectivity, substituent and solvent effects, and activation parameters, suggest that these reactions occur via a synchronous concerted mechanism on both competing pathways. The experimental

  尽管E-2-芳基硝基乙烯具有多种亲电性，但它们与环戊二烯的[4 + 2]环加成反应仍导致相应的6-内-芳基-5-外-硝基降冰片烯和6-外-芳基-5-内-硝基降冰片烯唯一的反应产物。立体选择性，取代基和溶剂的作用以及活化参数表明，这些反应是通过同步竞争的机制在两个竞争途径上发生的。获得的实验结果与来自B3LYP / 6-31G（d）计算的数据一致。由于E-2-芳基硝基乙烯具有高亲电性，因此应将研究的反应视为极性[4 + 2]环加成反应。版权所有©2011 John Wiley＆Sons，Ltd.
• Secondary α-deuterium kinetic isotope effects in [2+4] cycloaddition of (E)-2-phenylnitroethene to cyclopentadiene
  作者：Magdalena Kwiatkowska、Radomir Jasiński、Maria Mikulska、Andrzej Barański

  DOI：10.1007/s00706-010-0292-6

  日期：2010.5

  AbstractSecondary α-deuterium kinetic isotope effects confirm that [2+4] cycloaddition between (E)-2-phenylnitroethene and cyclopentadiene occurs in concerted manner, on both the pathway leading to 6-endo-phenyl-5-exo-nitronorbornene and the pathway leading to the corresponding 6-exo-phenyl-5-endo-nitro isomer. According to Hammond terminology the transition states on competitive pathways should be

  摘要次生α-氘动力学同位素效应证实，（E）-2-苯基硝基乙烯与环戊二烯之间的[2 + 4]环加成反应同时发生在导致6-内-苯基-5-外-硝基降冰片烯的途径和该途径上产生相应的6-外-苯基-5-内-硝基异构体。根据Hammond的术语，竞争路径上的过渡状态应以对称的早期状态来考虑。 图形概要
• Chiral Octahedral Phosphano–Oxazoline Iridium(III) Complexes as Catalysts in Asymmetric Cycloaddition Reactions
  作者：Daniel Carmona、Joaquina Ferrer、Néstor Garcı́a、Paola Ramı́rez、Fernando J. Lahoz、Pilar Garcı́a-Orduña、Luis A. Oro

  DOI：10.1021/om301089c

  日期：2013.3.25

  The synthesis and characterization of cationic iridium(III) aqua complexes of the formula [IrH(H2O)(PN*)(PP)][SbF6]2 (PN* = chiral phosphano–oxazoline ligand; PP = diphosphane) as well as that of the OPOF2-containing complex [IrH(OPOF2)(PNiPr)(dppp)][SbF6] (10) are reported. The X-ray molecular structures of [IrH(H2O)(PNInd)(dppe)][SbF6]2 (1), [IrH(H2O)(PNInd)(dppen)][SbF6]2 (2), and 10a have been

  式[IrH（H 2 O）（PN *）（PP）] [SbF 6 ] 2（PN * =手性膦-恶唑啉配体； PP =二膦）的阳离子铱（III）水配合物的合成与表征还报道了含OPOF 2的配合物[IrH（OPOF 2）（PN i Pr）（dppp）] [SbF 6 ]（10）。[IrH（H 2 O）（PNInd）（dppe）] [SbF 6 ] 2（1），[IrH（H 2 O）（PNInd）（dppen）] [SbF 6 ] 2（2）和10a已经确定。这些水性络合物的二氯甲烷溶液有效地催化硝酮的对映选择性1,3-偶极环加成Ñ -benzylidenephenylamine Ñ氧化物到环戊二烯和异丁烯之间和狄尔斯-阿尔德反应的反式-β-硝基苯乙烯。在第一种情况下，催化反应以极好的内选择性和ee高达85％进行；的Diels-Alder反应在室温下具有良好的快速发生内型：外型选择性和EE高达90％。偶