1-(2-methylphenyl)-2-nitropropan-1-ol

• 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: 1-(2-methylphenyl)-2-nitropropan-1-ol
• 英文别名: 2-nitro-1-o-tolylpropan-1-ol
• 化学式: C₁₀H₁₃NO₃
• 分子量: 195.218
• InChiKey: QHHPHQSIPASCSR-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.6
• 重原子数：
  14
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.4
• 拓扑面积：
  66
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为产物：
  描述：

  2-甲基苯甲醛 、 硝基乙烷 在 三乙胺 作用下， 以 二氯甲烷 为溶剂， 反应 20.0h， 生成 1-(2-methylphenyl)-2-nitropropan-1-ol
  参考文献：
  名称：

  Negative ion mass spectra of β-nitroalcohols

  摘要：

  DOI：

  10.1002/oms.1210241110

文献信息

• A Highly<i>anti</i>-Selective Asymmetric Henry Reaction Catalyzed by a Chiral Copper Complex: Applications to the Syntheses of (+)-Spisulosine and a Pyrroloisoquinoline Derivative
  作者：Kun Xu、Guoyin Lai、Zhenggen Zha、Susu Pan、Huanwen Chen、Zhiyong Wang

  DOI：10.1002/chem.201201775

  日期：2012.9.24

  A highly anti‐selective asymmetric Henry reaction has been developed, affording synthetically versatile β‐nitroalcohols in a predominately anti‐selective manner (mostly above 15:1) and excellent ee values (mostly above 95 %). Moreover, the anti‐selective Henry reaction was carried out in the presence of water for the first time with up to 99 % ee. The catalytic mechanism was proposed based on the detection

  已经开发出了一种高度抗选择性的不对称亨利反应，以一种主要是抗选择性的方式（大多数在15：1以上）和出色的ee值（大多数在95％以上）提供了合成通用的β-硝基醇。此外，抗选择性亨利反应是在水的存在下首次以高达99％  ee的条件进行的。基于萃取电喷雾电离质谱（EESI-MS）对中间体的检测，提出了催化机理。此外，抗加合物已成功转化为具有生化重要性的（+）-螺旋甜菜碱和吡咯并异喹啉衍生物。
• 2-Dihydromethylpiperazinediium-M^II(M^II= Cu^II, Fe^II, Co^II, Zn^II) double sulfates and their catalytic activity in diastereoselective nitroaldol (Henry) reaction
  作者：Houcine Naïli、Fadhel Hajlaoui、Tahar Mhiri、Tatiana C. O. Mac Leod、Maximilian N. Kopylovich、Kamran T. Mahmudov、Armando J. L. Pombeiro

  DOI：10.1039/c2dt31300f

  日期：——

  A series of double dihydromethylpiperazinediium metallic sulfates 1–7 [H2mpz]MII(SO4)2·nH2O (mpz = 2-methylpiperazine, C5H12N2) are prepared by slow evaporation using a racemic (R/S)-mpz (for 1, 2) or enantiopure R-mpz (for 3), S-mpz (for 4–7) and sulfates of CuII (for 5), FeII (for 1, 4), CoII (for 7) and ZnII (for 2, 3, 6), and characterized by infrared spectroscopy, elemental analysis and single crystal X-ray diffraction. The [MII(H2O)6]2+, [(R/S)-H2mpz]2+, [(R)-H2mpz]2+ or [(S)-H2mpz]2+ cations and 2SO42− anions are linked together via two types of hydrogen bonds, Ow–Hw⋯O and N–H⋯O, leading to supramolecular arrangements. The use of the racemic 2-mpz provides alternatives in crystallization: a centrosymmetric structure where the enantiomers are related by an appropriate crystallographic symmetry operation or one where the enantiomers occupy the same crystallographic position, generating disorder. Compounds 1–7 act as diastereoselective catalysts for the nitroaldol (Henry) reaction. The diastereoselectivity can be regulated from exclusive threo to exclusive erythro isomer preparation with typical yields of 50–99%, depending on the catalyst and the substrate used.

  一系列双二氢甲基哌嗪二铵金属硫酸盐1–7 [H2mpz]MII(SO4)2·nH2O（mpz = 2-甲基哌嗪，C5H12N2）通过缓慢蒸发法制备，使用了外消旋（R/S）-mpz（用于1、2）或对映体纯的R-mpz（用于3）、S-mpz（用于4–7）和洛铁（用于1、4）、铜（用于5）、钴（用于7）和锌（用于2、3、6）的硫酸盐，并通过红外光谱、元素分析和单晶X射线衍射进行表征。 [MII(H2O)6]2+、[(R/S)-H2mpz]2+、[(R)-H2mpz]2+或[(S)-H2mpz]2+阳离子与2SO42−阴离子通过两种类型的氢键（Ow–Hw⋯O和N–H⋯O）相互连接，形成超分子结构。使用外消旋的2-mpz提供了结晶方面的选择：一个中心对称结构，其中对映体通过适当的晶体对称操作相关联，或一个对映体占据相同的晶体位置，产生无序。化合物1–7作为氮丙醇（亨利）反应的二叠体选择性催化剂。二叠体选择性可从独占的threo异构体调节到独占的erythro异构体制备，典型产率为50–99%，取决于所使用的催化剂和底物。
• <i>anti</i>-Selective Asymmetric Henry Reaction Catalyzed by a Heterobimetallic Cu–Sm–Aminophenol Sulfonamide Complex
  作者：Yang Li、Ping Deng、Youmao Zeng、Yan Xiong、Hui Zhou

  DOI：10.1021/acs.orglett.6b00432

  日期：2016.4.1

  A novel heterobimetallic Cu/Sm/aminophenol sulfonamide complex has been developed by a convenient one-pot method for the anti-selective asymmetric Henry reaction. The corresponding anti-β-nitro alcohols are obtained in up to 99% yield, >30:1 dr, and 98% ee. The results of control experiments and ESI-MS analysis of the complex indicate that the monomeric bimetallic Cu/Sm/1 complex would be the active

  通过方便的一锅法开发了一种新型的双金属Cu / Sm /氨基苯酚磺酰胺络合物，用于抗选择性不对称亨利反应。以高达99％的收率，＞ 30∶1的dr和98％的ee获得相应的抗-β-硝基醇。配合物的对照实验和ESI-MS分析结果表明，单体双金属Cu / Sm / 1配合物是活性物质。
• Binaphthyl-Proline Hybrid Chiral Ligands: Modular Design, Synthesis, and Enantioswitching in Cu(II)-Catalyzed Enantioselective Henry Reactions
  作者：Chao Yao、Yaoqi Chen、Chao Wang、Ruize Sun、Haotian Chang、Ruiheng Jiang、Lin Li、Xin Wang、Yue-Ming Li

  DOI：10.1021/acs.joc.2c01127

  日期：——

  Chiral O–N–N tridentate ligands were designed from proline and BINOL. Their design strategy and performance were evaluated using a copper(II)-catalyzed asymmetric Henry reaction as a model. The desired β-nitroalcohols were obtained in up to 94% ee’s. Preliminary results suggested that the stereofacial selection of the reactions was mainly controlled by the chiral diamine moiety derived from proline

  手性 O-N-N 三齿配体是由脯氨酸和 BINOL 设计的。使用铜（II）催化的不对称亨利反应作为模型评估了他们的设计策略和性能。获得了所需的 β-硝基醇，其 ee 高达 94%。初步结果表明，反应的立体选择性主要受脯氨酸衍生的手性二胺部分控制，中心手性和轴向手性的匹配对于反应的高立体选择性至关重要。当适当的取代基被引入联萘基时，观察到对映体转换。在使用不带 3 个取代基的2a作为手性配体的反应中发现了Si选择，而Re-当使用带有3-三氟甲基的2i作为手性配体时，发现具有相同的高对映选择性。
• A Heterobimetallic Pd/La/Schiff Base Complex foranti-Selective Catalytic Asymmetric Nitroaldol Reactions and Applications to Short Syntheses of β-Adrenoceptor Agonists
  作者：Shinya Handa、Keita Nagawa、Yoshihiro Sohtome、Shigeki Matsunaga、Masakatsu Shibasaki

  DOI：10.1002/anie.200705617

  日期：2008.4.14