(E)-3-(4-bromophenyl)-2-nitroprop-2-en-1-ol | 1019636-30-6

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 肉桂醇
• 英文名称: (E)-3-(4-bromophenyl)-2-nitroprop-2-en-1-ol
• CAS: 1019636-30-6
• 化学式: C₉H₈BrNO₃
• 分子量: 258.071
• InChiKey: VVYJDSPYJLQYQD-WEVVVXLNSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2
• 重原子数：
  14
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.11
• 拓扑面积：
  66
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (E)-3-(4-bromophenyl)-2-nitroprop-2-en-1-ol 在 potassium carbonate 、 三乙胺 作用下， 以 乙醚 为溶剂， 生成 r-5',trans-6'-(4-bromophenyl)-1-methyl-cis-7'-nitro-7',8'-dihydro-6'H-spiro[indoline-3,5'-indolizin]-2-one
  参考文献：
  名称：

  仲胺-方酰胺促进的 Michael/Friedel-Crafts 多米诺反应立体控制构建含螺吲哚的 5,6,7,8-四氢吡咯并[1,2-a]吡啶

  摘要：

  已开发出一种使用 Morita-Baylis-Hillman (MBH) 硝基烯丙酯和 3-吡咯吲哚的不对称 Michael/Friedel-Crafts 级联反应，用于立体选择性构建含螺吲哚的四氢吲嗪。一系列具有三个连续手性中心（包括全碳四元立构中心）的四环支架以 53-85% 的分离产率生成，具有高非对映选择性和对映体纯度（≥3:1 dr，50-98% ee）。新合成的双功能仲胺/方酰胺有机催化剂被证明比其三级类似物表现出更好的立体化学控制。

  DOI：

  10.1021/acs.orglett.4c00073
• 作为产物：
  描述：

  2-硝基乙醇 、 对溴苯甲醛 在 sodium hydroxide 、 盐酸 作用下， 以 甲醇 、 水 为溶剂， 反应 14.33h， 以34%的产率得到(E)-3-(4-bromophenyl)-2-nitroprop-2-en-1-ol
  参考文献：
  名称：

  Synthesis, Structure, and E−Z Isomerization of β-(Hetero)aryl-α-nitro-α,β-enals

  摘要：

  The first general methodology for the gram-scale preparation of previously overlooked beta-(hetero)aryl-alpha-nitro-alpha,beta-enals (3) is reported. Condensation of (hetero) aromatic aldehydes with 2-nitroethanol gave the E-isomers of uncommon beta-(hetero)aryl-alpha-hydroxymethyl-alpha,beta-unsatured-nitroalkenes (2), as determined by NOE and X-ray studies. alpha-Nitro-alpha,beta-enals 3 were subsequently obtained by hypervalent iodine oxidation of 2 as E-Z-mixtures in solid form. They showed varied stability and solvent-dependent thermal-promoted and photopromoted E-Z interconversion. Starting with furfural, experimental conditions were developed to prepare the corresponding nitroenal 3a enriched in either the E or the Z isomer: E-3a/Z-3a approximate to 90/10 and 20/80, respectively. In contrast with other structurally related compounds, nitroenals 3 have their (hetero)aryl-vinyl unit and their formyl and nitro groups all in a planar arrangement, both in solid form and in solution; accordingly, they are colored compounds with predicted high dipole moments. As deduced from solution-NMR and X-ray data, the C=C and the C=O double bonds in 3 are exclusively s-cis-oriented; this disposition corresponds in fact to the DFT-computed most stable conformer.

  DOI：

  10.1021/jo702731b

文献信息

• [EN] PROCESSES FOR THE PREPARATION OF PANCRATISTATIN AND PANCRATISTATIN ANALOGUES<br/>[FR] PROCÉDÉS DE PRÉPARATION DE PANCRATISTATINE ET D'ANALOGUES DE PANCRATISTATINE
  申请人：UNIV SANTIAGO COMPOSTELA

  公开号：WO2009026961A1

  公开（公告）日：2009-03-05

  Processes for the preparation of pancratistatin and pancratistatin analogues. The key step is the reaction of a 1,3-dioxan-5-one and a nitroolefine in the presence of an amine. The process may take place in an enantioselective way when a chiral amine is used. Reduction processes then give new and advanced intermediates that are useful for the preparation of pancratistatin or selected pancratistatin analogues. The reported process also provides a method for the efficient synthesis of nitroenals, starting materials of the synthesis. Analogues of pancratistatin are also provided.

  制备pancratistatin和pancratistatin类似物的过程。关键步骤是在胺的存在下，将1,3-二氧杂环戊酮和硝基烯烃进行反应。当使用手性胺时，该过程可能以对映选择性方式进行。然后，还可以通过还原过程得到新的和先进的中间体，这些中间体对于制备pancratistatin或选定的pancratistatin类似物非常有用。报告的过程还提供了一种高效合成硝基烯醛的方法，这是合成的起始材料。还提供了pancratistatin的类似物。
• Organocatalytic Cascade Reactions: Towards the Diversification of Hydroisochromenes and Chromenes through Two Different Activation Modes
  作者：David Cruz Cruz、Rasmus Mose、Clarisa Villegas Gómez、Stine V. Torbensen、Martin S. Larsen、Karl Anker Jørgensen

  DOI：10.1002/chem.201403505

  日期：2014.9.1

  The organocatalytic enantioselective syntheses of functionalized hydroisochromenes and chromenes by trienamine‐mediated [4+2]‐cycloaddition/nucleophilic ring‐closing and iminium‐ion/aminal‐mediated oxa‐Michael/Michael/nucleophilic ring‐closing with 2‐nitroallylic alcohols are presented. The corresponding cycloadducts, with up to five stereocenters, are formed in good yield and excellent enantioselectivities

  介绍了由三烯胺介导的[4 + 2]-环加成/亲核开环和亚胺离子/氨基介导的氧杂-Michael / Michael /亲核与2-硝基烯丙醇成环的功能化氢异色酮和色烯的有机催化对映选择性合成。 。形成具有最多五个立体中心的相应的环加合物，具有良好的产率和优异的对映选择性。已经证明了所得产物的合成应用。
• Organocatalytic desymmetrization of cyclic meso-anhydrides through enantioselective alcoholysis with functionalized primary nitroallylic alcohols
  作者：Yan ming Chen、Mamatha Amireddy、Kwunmin Chen

  DOI：10.1016/j.tet.2014.10.008

  日期：2014.11

  The direct organocatalytic desymmetrization of cyclic meso-anhydrides was achieved by alcoholysis with nitroallylic alcohols. The reaction between primary nitroallylic alcohols and cyclic meso-anhydrides catalyzed by cinchonidine derived thiourea organocatalyst II (10 mol %) proceeded smoothly. The corresponding hemiesters were obtained in high chemical yields with high to excellent levels of stereoselectivity

  环状内消旋酸酐的直接有机催化去对称化是通过用硝基烯丙醇进行醇解而实现的。由辛可尼定衍生的硫脲有机催化剂II（10 mol％）催化的伯硝基烯丙醇与环状内消旋酸酐的反应进行得很顺利。相应的半酯以高化学产率获得，具有高至极好的立体选择性水平（高达90％的收率和99％的ee）。另一方面，当氨基辛可尼定衍生物（III）在类似反应条件下用作有机催化剂时，观察到对映选择性的逆转。这证明了在环的去对称化中亲核组分的活化的例子。内消旋酸酐。
• A remarkable solvent effect on the reaction of 4-hydroxycoumarin with (E)-3-aryl-2-nitroprop-2-enol: Facile synthesis of highly substituted furo/pyrano[3,2-c]chromenes
  作者：Shivendra Singh、Anvita Srivastava、Shaikh M. Mobin、Sampak Samanta

  DOI：10.1039/c4ra10610e

  日期：——

  A remarkable solvent effect on the reaction of 4-hydroxycoumarin derivatives with (E)-3-aryl/hetero-aryl-2-nitroprop-2-enols has been observed in water and DMSO media. This result was employed for the straightforward syntheses of new functionalized furo/pyrano[3,2-c]chromenes in 63–93% yields and diasteromeric ratio up to ≤99 : 1. Moreover, a simple, mild, efficient and catalyst-free one-pot method

  在水和DMSO介质中，已观察到对4-羟基香豆素衍生物与（E）-3-芳基/杂芳基-2-硝基丙-2-烯醇的反应具有显着的溶剂作用。该结果用于新型官能化的呋喃/吡喃并[3,2- c ]色烯的直接合成，产率为63-93％，非对映异构体比例最高为≤99：1。此外，该方法简单，温和，高效且无催化剂一锅法可能会为香豆素核上的呋喃/吡喃环的成环提供另一种合成策略。此外，水对该反应的速率和选择性（产物）显示出显着的积极作用。
• Organocatalytic Enantioselective Michael-Henry Acetalization of Glutaraldehyde and 3-Aryl-2-nitroprop-2-enols: A Facile Entry to 3-Oxabicyclo[3.3.1]nonan-2-ones with Four Consecutive Stereogenic Centers
  作者：Bor-Cherng Hong、Ding-Jyun Lan、Nitin S. Dange、Gene-Hsiang Lee、Ju-Hsiou Liao

  DOI：10.1002/ejoc.201201496

  日期：2013.4

  A convenient method was developed for the enantioselective (>99 % ee) synthesis of 3-oxabicyclo[3.3.1]nonan-2-ones containing four consecutive stereogenic centers. The method comprises a cascade organocatalytic Michael–Henry acetalization–oxidation reaction of glutaraldehyde and 3-aryl-2-nitroprop-2-enols. The structures and absolute configurations of the products were confirmed by X-ray analysis.

  为对映选择性 (>99% ee) 合成包含四个连续立体中心的 3-oxabicyclo[3.3.1]nonan-2-ones 开发了一种方便的方法。该方法包括戊二醛和 3-芳基-2-硝基丙-2-烯醇的级联有机催化迈克尔-亨利缩醛化-氧化反应。X射线分析证实了产物的结构和绝对构型。