2-(2,2-dibromovinyl)-4-methoxyphenol | 1378942-37-0

• 分子结构分类: 有机化合物 - 苯类化合物 - 酚类
• 英文名称: 2-(2,2-dibromovinyl)-4-methoxyphenol
• 英文别名: 2-(2,2-Dibromoethenyl)-4-methoxyphenol；2-(2,2-dibromoethenyl)-4-methoxyphenol
• CAS: 1378942-37-0
• 化学式: C₉H₈Br₂O₂
• 分子量: 307.969
• InChiKey: DCDIOTQXYRBZFY-UHFFFAOYSA-N

物化性质

• 沸点：
  371.9±37.0 °C(Predicted)
• 密度：
  1.895±0.06 g/cm3(Temp: 20 °C; Press: 760 Torr)(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.6
• 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：
  29.5
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  2-(2,2-dibromovinyl)-4-methoxyphenol 在 (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride 、 potassium fluoride 、 copper(l) iodide 、 三溴化硼 、 caesium carbonate 作用下， 以 1,4-二氧六环 、 乙醇 、 二氯甲烷 为溶剂， 反应 20.0h， 生成 2-(4-hydroxyphenyl)benzofuran-5-ol
  参考文献：
  名称：

  Design and synthesis of 2-phenylnaphthalenoids and 2-phenylbenzofuranoids as DNA topoisomerase inhibitors and antitumor agents

  摘要：

  Eight 2-phenylnaphthalenoids (2PNs) (3a h) and twenty four 2-phenylbenzofuranoids (2PBF5) (4a-4j, 5a-5j, 6a, 6f-6h) were successfully designed, synthesized and their antiproliferative and in vitro DNA topoisomerase inhibitory activities were evaluated. Nine compounds (four 2PNs and five 2PBFs) showed either Topol or TopoII alpha inhibitory activities. Six compounds (four 2PNs and two 2PBFs) exhibited potent cytotoxicity with IC50 values for 72 h exposure ranging from 0.3 to above 20 mu M against MDA-MB-231, MDA-MB-435, HepG2 and PC3 cell lines. The two 2PBFs displayed comparable and even better antiproliferative as well as TopoII alpha inhibitory activities than 2PNs. Interestingly, the active 2PBFs displayed different mechanisms of TopoII alpha inhibition from that of 2PNs, suggesting that the chromophore scaffold replacement may result in a change of the binding site of inhibitors to TopoII alpha. Furthermore, the mechanisms of antiproliferation on MDA-MB-231 cells indicate that compounds 5a and 5f are promising for further development of anticancer agents. The results of this study reveal that the evolutionary strategy of medicinal chemistry through scaffold hopping is a promising strategy for structure optimization of TopoII alpha inhibitors. (C) 2015 Elsevier Masson SAS. All rights reserved.

  DOI：

  10.1016/j.ejmech.2015.07.048
• 作为产物：
  描述：

  2-羟基-5-甲氧基苯甲醛 、 四溴化碳 在 三乙胺 、 三苯基膦 作用下， 以 二氯甲烷 为溶剂， 以72 %的产率得到2-(2,2-dibromovinyl)-4-methoxyphenol
  参考文献：
  名称：

  钯催化合成连接双杂环─合成及光物理性质研究

  摘要：

  报道了钯催化的多米诺骨牌 C-N 偶联/Cacchi 反应。在密度泛函理论计算的辅助下，进行了光致发光双杂环的设计，合成收率高达 98%。通过该策略获得的产品的光物理特性是一项综合研究的一部分，该研究导致了宽发射光谱和高达 0.59 的量子产率。机理实验证实溴炔是有效的中间体，密度泛函理论研究表明了一条涉及初始氧化加成到偕二卤代烯烃的顺式 C-Br 键的途径。

  DOI：

  10.1021/jacs.3c07234

文献信息

• An efficient tandem elimination–cyclization–desulfitative arylation of 2-(gem-dibromovinyl)phenols(thiophenols) with sodium arylsulfinates
  作者：Wei Chen、Pinhua Li、Tao Miao、Ling-Guo Meng、Lei Wang

  DOI：10.1039/c2ob27232f

  日期：——

  An efficient tandem elimination–cyclization–desulfitative arylation of 2-(gem-dibromovinyl)phenols(thiophenols) with sodium arylsulfinates has been developed. In the presence of TBAF–PdCl2–Cu(OAc)2–NEt3, the reactions generated 2-arylbenzofurans(thiophenes) with good yields in one-pot under ligand-free conditions.

  开发了一种高效的串联去除、环化和去亚磺酰化芳基化反应，利用2-(gem-二溴乙烯基)酚（硫酚）与芳基亚磺酸钠反应。在TBAF–PdCl2–Cu(OAc)2–NEt3的催化下，该反应在无配体条件下以一锅法生成了产率良好的2-芳基苯并呋喃（硫烯）。
• Tandem Synthesis of 2-Carboxybenzofurans <i>via</i> Sequential Cu-Catalyzed C–O Coupling and Mo(CO)₆-Mediated Carbonylation Reactions
  作者：Qinliang Mo、Nan Sun、Liqun Jin、Baoxiang Hu、Zhenlu Shen、Xinquan Hu

  DOI：10.1021/acs.joc.0c01620

  日期：2020.9.4

  A modular tandem synthesis of 2-carboxybenzofurans from 2-gem-dibromovinylphenols has been established based on a sequence of Cu-catalyzed intramolecular C–O coupling and Mo(CO)6-mediated intermolecular carbonylation reactions. This protocol allowed one-step access to a broad variety of functionalized benzofuran-2-carboxylic acids, esters, and amides in good to excellent yields under Pd- and CO gas-free

  由2- 2-羧基苯并呋喃的模块化串联合成宝石-dibromovinylphenols已经基于Cu催化的分子内CO耦合和Mo（CO）的序列被建立6个介导的分子间羰基化反应。该方案允许在无Pd和CO气体条件下以良好至极佳的收率一步一步获得各种官能化的苯并呋喃-2-羧酸，酯和酰胺。
• Synthesis of Diversely Functionalized 2<i>H</i>-Chromenes through Pd-Catalyzed Cascade Reactions of 1,1-Dibromoolefin Derivatives with Arylboronic Acids
  作者：Xia Song、Cai Gao、Xinying Zhang、Xuesen Fan

  DOI：10.1021/acs.joc.8b02456

  日期：2018.12.21

  this work, an unprecedented synthesis of (2H-chromen-2-ylidene)acetates and (2H-chromen-2-ylidene)ethanones with controlled stereoselectivity via Pd-catalyzed cascade reactions of 3-(2-(2,2-dibromovinyl)phenoxy)acrylates or 3-(2-(2,2-dibromovinyl)phenoxy)enones with aryl boronic acids has been established. This protocol combines two C–C bond forming reactions (an intermolecular Suzuki coupling followed

  在这项工作中，（2的前所未有的合成ħ -色烯-2-亚基）乙酸盐和（2- ħ -色烯-2-亚基）通过3-（2- Pd-催化级联反应具有受控立体选择性ethanones（2,2-已经建立了具有芳基硼酸的-二溴乙烯基）苯氧基）丙烯酸酯或3-（2-（2,2-二溴乙烯基）苯氧基）烯酮。该方案在同一催化剂的催化下，在一个罐中结合了两个C–C键形成反应（分子间Suzuki偶联，然后是分子内Heck偶联）。与文献中制备2 H的方法比较-色烯衍生物，具有诸如容易获得或可商购的底物，产品的多种取代模式，简单的方法和优异的立体选择性等优点。有趣的是，这种级联反应可以区分吸电子能力和各种官能团大小的细微差别，从而导致不同的化学选择性。另外，如此获得的（2 H-铬-2-亚甲基）乙酸酯的实用性通过其向合成和光物理上显着的3 H-黄嘌呤-3-酮衍生物的容易转化而得以展示。
• A highly efficient one-pot reaction of 2-(gem-dibromovinyl)phenols(thiophenols) with K4Fe(CN)6 to 2-cyanobenzofurans(thiophenes)
  作者：Wei Zhou、Wei Chen、Lei Wang

  DOI：10.1039/c2ob25356a

  日期：——

  2-Cyanobenzofurans and 2-cyanobenzothiophenes were prepared through an efficient one-pot Ullmann-reaction/cyanation reaction. In the presence of CuI/Na2CO3–Pd(OAc)2/PPh3 in DMF, the reaction of 2-(gem-dibromovinyl)phenols and 2-(gem-dibromovinyl)thiophenols with K4Fe(CN)6, as non-toxic and user-friendly cyanating reagent, proceeded smoothly to generate the corresponding 2-cyanobenzofurans and 2-cyanobenzothiophenes

  通过有效的一锅Ullmann反应/氰化反应制备2-氰基苯并呋喃和2-氰基苯并噻吩。在DMF中CuI / Na 2 CO 3 -Pd（OAc）2 / PPh 3的存在下，2-（宝石-二溴乙烯基）苯酚和2-（宝石-二溴乙烯基）苯硫酚与K 4 Fe（CN）6的反应作为无毒且对用户友好的氰化试剂，该试剂可顺利进行，以高收率生成相应的2-氰基苯并呋喃和2-氰基苯并噻吩。
• Synthesis of 2-selenyl(sulfenyl)benzofurans via Cu-catalyzed tandem reactions of 2-(gem-dibromovinyl)phenols with diorganyl diselenides(disulfides)
  作者：Jie Liu、Wei Chen、Lei Wang

  DOI：10.1039/c3ra23361h

  日期：——

  An efficient synthesis of 2-selenyl(sulfenyl)benzofurans has been accomplished through a copper(I)-catalyzed tandem reaction of 2-(gem-dibromovinyl)phenols with diorganyl diselenides and disulfides in the presence of CuI/Mg/t-BuOLi in DMSO. Using this protocol, a variety of 2-selenyl(sulfenyl)benzofuran derivatives were obtained in good yields.

  已通过铜(I)催化的串联反应，高效合成了2-硒基（硫醇基）苯并呋喃，该反应是将2-（gem-二溴乙烯基）苯酚与二有机基二硒化物和二硫化物在CuI/Mg/t-BuOLi的存在下于DMSO中进行的。采用该方法，获得了多种2-硒基（硫醇基）苯并呋喃衍生物，产率良好。