(5-fluoropentyl)zinc(II) bromide | 1037176-29-6

• 分子结构分类: 有机化合物 - 有机金属化合物 - 金属烷基卤化物
• 英文名称: (5-fluoropentyl)zinc(II) bromide
• 英文别名: (5-fluoropentyl)zinc bromide
• CAS: 1037176-29-6
• 化学式: C₅H₁₀BrFZn
• 分子量: 234.427
• InChiKey: SHOMYZGDVNYBNF-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  2.94
• 重原子数：
  8.0
• 可旋转键数：
  5.0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  0.0
• 氢给体数：
  0.0
• 氢受体数：
  0.0

反应信息

• 作为反应物：
  描述：

  (5-fluoropentyl)zinc(II) bromide 、 1-(3,5-di-O-benzoyl-2-deoxy-2-fluoro-β-D-arabinofuranosyl)-N³-benzoyl-5-iodouracil 在 二(三叔丁基膦)钯 作用下， 以 N,N-二甲基乙酰胺 为溶剂， 生成 3-N-benzoyl-3',5'-di-O-benzoyl-5-(5-fluoropentyl)-2'-deoxy-2'-fluoroarabinouridine
  参考文献：
  名称：

  Synthesis and in Vitro Evaluation of 5-[¹⁸F]Fluoroalkyl Pyrimidine Nucleosides for Molecular Imaging of Herpes Simplex Virus Type 1 Thymidine Kinase Reporter Gene Expression

  摘要：

  Two novel series of 5-fluoroalkyl-2'-deoxyuridines (FPrDU, FBuDU, FPeDU) and 2'-fluoro-2'-deoxy-5-fluoroalkylarabinouridines (FFPrAU, FFBuAU, FFPeAU) that have three, four, or five methylene units (propyl, butyl, or pentyl) at C-5 were prepared and tested as reporter probes for imaging herpes simplex virus type I thymidine kinase (HSV1-tk) gene expression. The Negishi coupling methodology was employed in efficiently synthesizing the radiolabeling precursors. All six 5-[F-18]fluoroalkyl pyrimidines were readily prepared from 3-N-benzoyl-3',5'-di-O-benzoyl-protected 5-O-mesylate Precursors in 17-35% radiochemical yield (decay-corrected). In vitro studies highlighted that all six [F-18]-labeled nucleosides selectively accumulated in cells expressing the HSV1-TK protein and there was negligible uptake in control cells. [F-18]FPrDU, [F-18]FBuDU, [F-18]FPeDU, and [F-18]FFBuAU had the best uptake profiles. Despite their selective accumulation in HSV1-tk-expressing cells, all 5-fluoroalkyl pyrimidine nucleosides had low-to-negligible cytotoxic activity (CC50 > 1000-1209 mu M). Ultimately, the results demonstrated that 5-[F-18]fluoropropyl, [F-18]fluorobutyl, and [F-18]fluoropentyl pyrimidine nucleosides have the potential to be in vivo HSV1-TK PET reporter probes over a dynamic range of reporter gene expression levels.

  DOI：

  10.1021/jm800501d
• 作为产物：
  描述：

  1-溴-5-氟戊烷 、 锌 在 碘 作用下， 以 N,N-二甲基乙酰胺 为溶剂， 反应 10.0h， 生成 (5-fluoropentyl)zinc(II) bromide
  参考文献：
  名称：

  通过 α-氧-乙烯基砜与烷基锌试剂的镍催化交叉偶联选择性合成烯醇醚

  摘要：

  我们在这里描述了一种 Ni 催化的 Negishi 偶联反应，以立体会聚的方式制备 1,2-二烷基烯醇醚。该方法使用容易获得且工作台稳定的 α-氧-乙烯基砜作为亲电试剂。在这些反应中，α-氧-乙烯基砜基序中的 C-砜键被化学选择性地裂解。温和的条件可以容忍双方的各种官能团，因此代表了烯醇醚合成的一般策略。α-氧-乙烯基砜的这种独特的反应性表明它们在交叉偶联反应中作为亲电伙伴的进一步应用。

  DOI：

  10.1039/d1cc05347g

文献信息

• Palladium-Catalyzed Secondary Benzylic Imidoylative Reactions
  作者：Chenglong Wang、Licheng Wu、Wentao Xu、Feng He、Jingping Qu、Yifeng Chen

  DOI：10.1021/acs.orglett.0c02515

  日期：2020.9.4

  Reported herein is a palladium-catalyzed secondary benzylic imidoylative Negishi reaction leveraging the sterically bulky aromatic isocyanides as the imine source. This method allows the facile access of alkyl-, (hetero)aryl-, and alkynylzinc reagents to afford various α-substituted phenylacetone products under mild acidic hydrolysis, which are ubiquitous motifs in many pharmaceuticals and biologically

  本文报道了利用空间上庞大的芳族异氰酸酯作为亚胺源的钯催化的仲苄基亚氨基酰亚胺化Negishi反应。该方法允许在温和的酸性水解条件下容易地获得烷基，（杂）芳基和炔基锌试剂，从而得到各种α-取代的苯丙酮产物，这些产物是许多药物和生物活性化合物中普遍存在的基序。亚胺的非对映选择性还原可以实现，以将仲苄基卤化物方便地转化为具有高原子经济性的α-取代的苯乙胺衍生物。
• Direct Transformation of Aryl 2-Pyridyl Esters to Secondary Benzylic Alcohols by Nickel Relay Catalysis
  作者：Xianqing Wu、Xiaobin Li、Wenyi Huang、Yun Wang、Hui Xu、Liangzhen Cai、Jingping Qu、Yifeng Chen

  DOI：10.1021/acs.orglett.9b00774

  日期：2019.4.5

  secondary benzylic alcohols via tandem Ni-catalyzed cross-coupling reactions of aromatic 2-pyridyl esters with alkyl zinc reagents and carbonyl group reduction by Ni–H species is achieved. Preliminary mechanistic studies reveal that the Ni–H species is generated in situ via β-hydride elimination of the Negishi reagents. The reaction is catalyzed by bench-stable nickel salts under mild conditions with

  通过芳族2-吡啶酯与烷基锌试剂的串联Ni催化的交叉偶联反应，以及Ni-H物种还原的羰基，可以将芳基酯直接转化为仲苄醇。初步的机理研究表明，Ni-H物种是通过Negishi试剂的β-氢化物消除原位生成的。在温和的条件下，具有稳定的官能团耐受性，可通过稳定的镍盐催化该反应。
• Enantioconvergent Cross‐Couplings of Alkyl Electrophiles: The Catalytic Asymmetric Synthesis of Organosilanes
  作者：Gregg M. Schwarzwalder、Carson D. Matier、Gregory C. Fu

  DOI：10.1002/anie.201814208

  日期：2019.3.11

  Metal-catalyzed enantioconvergent cross-coupling reactions of alkyl electrophiles are emerging as a powerful tool in asymmetric synthesis. To date, high enantioselectivity has been limited to couplings of electrophiles that bear a directing group or a proximal p/π orbital. Herein, we demonstrate for the first time that enantioconvergent cross-couplings can be achieved with electrophiles that lack such

  金属催化的烷基亲电子试剂的对映会聚交叉偶联反应正在成为不对称合成中的有力工具。迄今为止，高对映选择性仅限于带有导向基团或近端 p/π 轨道的亲电子试剂的偶联。在此，我们首次证明对映异构交叉偶联可以通过缺乏此类特征的亲电子试剂来实现；具体来说，我们确定手性镍催化剂可以在简单温和的条件下完成外消旋α-卤代硅烷与烷基锌试剂的根岸反应，具有良好的对映选择性，从而提供对映体富集的有机硅烷（一类重要的目标分子）的途径。
• Enantio- and Regioconvergent Synthesis of γ-Stereogenic Vinyl Germanes and Their Use as Masked Vinyl Halides
  作者：Daniel Brösamlen、Martin Oestreich

  DOI：10.1021/acs.orglett.3c00410

  日期：2023.3.24

  excellent yields and enantioselectivities. The reason for the regioconvergence is the steering effect of the bulky germyl group. The resulting vinyl germanes can be easily halodegermylated without racemization of the allylic stereocenter to afford synthetically valuable γ-stereogenic vinyl halides.

  报道了外消旋锗化烯丙基亲电子试剂与烷基亲核试剂的区域异构混合物的镍催化对映和区域收敛烷基化。成功的关键是新开发的 hept-4-yl 取代的 Pybox 配体，它能够以优异的产率和对映选择性获得各种手性 γ-甲锗烷基 α-烷基烯丙基结构单元。区域会聚的原因是庞大的甲锗烷基的转向作用。生成的乙烯基锗烷可以很容易地卤代去锗化，而无需烯丙基立构中心的外消旋化，从而提供具有合成价值的 γ-立体乙烯基卤化物。
• <scp>Nickel‐Catalyzed</scp> Regiodivergent Acylzincation of Styrenes with Organozincs and <scp>CO</scp>^†
  作者：Chenglong Wang、Ning Liu、Xianqing Wu、Jingping Qu、Yifeng Chen

  DOI：10.1002/cjoc.202300590

  日期：2024.3.15

  metal-catalyzed carbometallation of unsaturated hydrocarbons constitutes one of the most efficient synthetic methodologies for the construction of C—C bond. Recently, the incorporation of organometallic reagent with the CO gas as a nucleophilic acyl synthon could enable the acylmetallation reaction, which greatly increases the horizon of carbometallation chemistry. Herein, we report a nickel-catalyzed

  过渡金属催化不饱和烃的碳金属化是构建CC键最有效的合成方法之一。最近，将有机金属试剂与CO气体结合作为亲核酰基合成子可以实现酰基金属化反应，这极大地拓展了碳金属化化学的视野。在此，我们报道了镍催化的邻氰基肉桂酸酯和邻氰基苯乙烯的区域发散酰基化反应，其中氰基部分在分子内捕获锌中间体以触发串联环化过程。该方案具有条件温和、底物范围广和优异的官能团耐受性的特点，从而提供了多种高度功能化的碳环化合物。