(E)-1-(3-bromoprop-1-en-1-yl)-2-nitrobenzene | 443305-35-9

• 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: (E)-1-(3-bromoprop-1-en-1-yl)-2-nitrobenzene
• 英文别名: 2-nitrocinnamyl bromide；o-nitrocinnamyl bromide；1-(3-Bromo-1-propenyl)-2-nitrobenzene；1-[(1e)-3-Bromoprop-1-en-1-yl]-2-nitrobenzene；1-[(E)-3-bromoprop-1-enyl]-2-nitrobenzene
• CAS: 443305-35-9
• 化学式: C₉H₈BrNO₂
• 分子量: 242.072
• InChiKey: YGYUHOIYDZMTDT-HWKANZROSA-N

物化性质

• 沸点：
  330.5±30.0 °C(Predicted)
• 密度：
  1.557±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.7
• 重原子数：
  13
• 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：
  45.8
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (E)-1-(3-bromoprop-1-en-1-yl)-2-nitrobenzene 在 palladium on activated charcoal 氢气 、 羟胺 、 sodium methylate 、 对甲苯磺酸 作用下， 以 N,N-二甲基甲酰胺 、 甲苯 为溶剂， 100.0 ℃ 、101.33 kPa 条件下， 生成 (R)-methyl 1-(2-aminophenyl)-8-ethyl-8-vinyl-5,6,7,8-tetrahydroindolizine-3-carboxylate
  参考文献：
  名称：

  (-)-Rhazinilam 的全合成：通过使用手性助剂进行不对称 C-H 键活化

  摘要：

  抗肿瘤剂 (-)-rhazinilam 在三个主要步骤中合成，即吡咯合成、选择性 C[键]H 键活化和直接大环内酰胺形成。关键步骤涉及中间体 6 中二乙基段的不对称 C[键]H 键官能化（脱氢）。这是通过将手性铂配合物连接到近端氮原子上来实现的。通过使用恶唑啉基酮手性助剂实现了高度的选择性 (60-75% ee)。

  DOI：

  10.1021/ja026130k
• 作为产物：
  描述：

  2-nitrocinnamaldehyde 在 sodium tetrahydroborate 、 三溴化磷 作用下， 以 甲醇 、 乙醚 为溶剂， 反应 0.5h， 生成 (E)-1-(3-bromoprop-1-en-1-yl)-2-nitrobenzene
  参考文献：
  名称：

  Novel Terminal Bipheny-Based Diapophytoene Desaturases (CrtN) Inhibitors as Anti-MRSA/VISR/LRSA Agents with Reduced hERG Activity

  摘要：

  CrtN has been identified as an attractive and druggable target for treating pigmented Staphylococcus aureus infections. More than 100 new compounds were synthesized, which target the overwhelming the defects of the CrtN inhibitor 1. Analogues 23a and 23b demonstrated a significant activity against pigmented S. aureus Newman and 13 MRSA strains (IC50 = 0.02-10.5 nM), along with lower hERG inhibition (IC50 > 30 mu M, similar to 10-fold decrease in comparison with 1). Furthermore, 23a and 23b were confirmed to reduce the staphylococcal load in the kidney and heart in a mouse model with normal treatment deeper than pretreatment ones, comparable even with vancomycin and linezolid. Remarkably, 23a could strongly block the pigment biosynthesis of these nine multidrug-resistant MRSA strains, including excellent activity against LRSA strains and VISA strains in vivo, and all of which demonstrated that 23a has a huge potential against intractable MRSA, VISA, and LRSA issues as a therapeutic drug.

  DOI：

  10.1021/acs.jmedchem.7b01300

文献信息

• Chiral Brønsted Acid Catalyzed Enantioselective Phosphonylation of Allylamine via Oxidative Dehydrogenation Coupling
  作者：Ming-Xing Cheng、Ran-Song Ma、Qiang Yang、Shang-Dong Yang

  DOI：10.1021/acs.orglett.6b01514

  日期：2016.7.1

  A new strategy for the synthesis of chiral α-amino phosphonates by enantioselective C–H phosphonylation of allylamine with phosphite in the presence of a chiral Brønsted acid catalyst has been developed. This protocol successfully integrates direct C–H oxidation with asymmetric phosphonylation and exhibits high enantioselectivity.

  在手性布朗斯台德酸催化剂的存在下，开发了一种通过烯丙基胺与亚磷酸酯的对映体C–H膦酰基对映体选择性合成手性α-氨基膦酸酯的新策略。该方案成功地将直接的C–H氧化与不对称的膦酰化反应相结合，并显示出高对映选择性。
• Copper(I) trifluoromethylthiolate complex bearing triphenylphosphine ligand for nucleophilic trifluoromethylthiolation of allylic bromides
  作者：Zhiyuan Wang、Qiqi Tu、Zhiqiang Weng

  DOI：10.1016/j.jorganchem.2013.08.008

  日期：2014.2

  crystallography. In the solid state, complex 1 exists as a monomeric copper(I) species with a three-coordinated trigonal planar geometry. Complex 1 reacted with a wide range of allylic bromides to afford corresponding allylic trifluoromethyl thioethers in moderate to good yields. Several functional groups, including alkyl, alkoxy, nitro, halides and geranyl groups, are tolerated.

  铜（I）三氟甲基硫醇铜络合物（PPh 3）2 Cu（SCF 3）（1）是由CuF 2与CF 3 SiMe 3和S 8在三苯基膦的存在下方便地反应合成的。配合物1的晶体结构已经通过X射线晶体学确定。在固态下，配合物1以具有三坐标三角平面几何形状的单体铜（I）形式存在。综合大楼1与各种烯丙基溴反应，以中等到良好的产率得到相应的烯丙基三氟甲基硫醚。可以耐受几个官能团，包括烷基，烷氧基，硝基，卤化物和香叶基。
• Nucleophilic Trifluoromethylthiolation of Allylic Bromides: A Facile Preparation of Allylic Trifluoromethyl Thioethers
  作者：Jianwei Tan、Guoting Zhang、Yangli Ou、Yaofeng Yuan、Zhiqiang Weng

  DOI：10.1002/cjoc.201300415

  日期：2013.7

  A facile preparation of allylic trifluoromethyl thioethers was achieved by using a copper reagent. The reaction of (bpy)Cu(SCF3) with various allylic bromides afforded the desired trifluoromethylthiolation products in good to excellent yields with high stereo‐ and regioselectivity. Common functional groups such as alkyl, alkoxy, trifluoromethyl, nitro, halides and geranyl are well tolerated.

  通过使用铜试剂可以容易地制备烯丙基三氟甲基硫醚。（bpy）Cu（SCF 3）与各种烯丙基溴的反应可提供所需的三氟甲基硫醇化产物，并具有良好的产率，以及高的立体选择性和区域选择性。常见的官能团如烷基，烷氧基，三氟甲基，硝基，卤化物和香叶基具有良好的耐受性。
• Direct bromocarboxylation of arynes using allyl bromides and carbon dioxide
  作者：Yu Zhang、Wenfang Xiong、Jinghe Cen、Wuxin Yan、Yaodan Wu、Chaorong Qi、Wanqing Wu、Huanfeng Jiang

  DOI：10.1039/c9cc05495b

  日期：——

  An unprecedented three-component coupling involving arynes, allyl bromides, and CO2 is described, providing efficient and facile access to structurally diverse ortho-brominated aryl esters. Unlike the conventional role played in organic synthesis as electrophiles, organic bromides served as nucleophiles in this reaction, affording a new approach to multicomponent reactions (MCRs) involving aryne intermediates

  描述了涉及芳烃，烯丙基溴和CO 2的空前的三组分偶联，提供了结构上多样化的邻溴代芳基酯的有效而便捷的途径。与有机合成中作为亲电试剂的常规作用不同，有机溴化物在该反应中充当亲核试剂，为涉及芳烃中间体的多组分反应（MCR）提供了新方法。另外，Hammett分析表明存在两种反应机理，这取决于所用肉桂基溴化物的电子性质。
• α,β-Unsaturated Gold(I) Carbenes by Tandem Cyclization and 1,5-Alkoxy Migration of 1,6-Enynes: Mechanisms and Applications
  作者：Pilar Calleja、Óscar Pablo、Beatrice Ranieri、Morgane Gaydou、Anthony Pitaval、María Moreno、Mihai Raducan、Antonio M. Echavarren

  DOI：10.1002/chem.201602347

  日期：2016.9.12

  1,6-Enynes bearing OR groups at the propargyl position generate α,β-unsaturated gold(I)-carbenes/ gold(I) stabilized allyl cations that can be trapped by alkenes to form cyclopropanes or 1,3-diketones to give products of α-alkylation. The best migrating group is p-nitrophenyl ether, which leads to the corresponding products without racemization. Thus, an improved formal synthesis of (+)-schisanwilsonene

  在炔丙基位置带有 OR 基团的 1,6-烯炔会生成 α,β-不饱和金 (I)-卡宾/金 (I) 稳定的烯丙基阳离子，这些阳离子可被烯烃捕获以形成环丙烷或 1,3-二酮，从而得到产品α-烷基化。最好的迁移基团是对硝基苯醚，它可以产生相应的产物而不会发生外消旋化。因此，已经完成了(+)-五味子烯A的改进形式合成。不同的竞争反应途径已通过计算描绘出来。