3-bromopropenyl acetate | 4957-34-0

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: 3-bromopropenyl acetate
• 英文别名: 3-bromo-1-acetoxy-1-propene；3-bromoprop-1-enyl acetate；3-Bromopropenyl acetate
• CAS: 4957-34-0
• 化学式: C₅H₇BrO₂
• 分子量: 179.013
• InChiKey: JJPZBCGMCATWNR-UHFFFAOYSA-N

物化性质

• 沸点：
  28-31 °C(Press: 35 Torr)
• 密度：
  1.435 g/cm3

计算性质

• 辛醇/水分配系数(LogP)：
  1
• 重原子数：
  8
• 可旋转键数：
  3
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.4
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  3-bromopropenyl acetate 在 N-碘代丁二酰亚胺 、 锌 作用下， 以 氯仿 、 N,N-二甲基甲酰胺 为溶剂， 反应 29.0h， 生成 Acetic acid (3S,4S,5R)-2-benzyl-5-iodomethyl-3-isobutyl-isoxazolidin-4-yl ester
  参考文献：
  名称：

  3-Bromo-propenyl acetate in organic synthesis: an expeditious route to 3-alkyl-4-acetoxy-5-iodomethyl isoxazolidines

  摘要：

  N-Trimethylsilyloxy-N-benzyl-1-alkyl-2-acetoxy-3-buten-1-amines 13, obtained in good yields and moderate diastereo-selectivities by TMSOTf promoted alpha-acetoxyallylation of nitrones using metallic zinc and 3-bromo-propenyl acetate 11, are exploited in a stereospecific 5-exo-trig iodocyclization reaction to afford 4,5-eis-3-alkyl-4-acetoxy-5-iodomethyl isoxazolidines 14, promising starting materials for the synthesis of pyrrolidine azasugars. (c) 2005 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetlet.2005.04.004
• 作为产物：
  描述：

  乙酰溴 、 丙烯醛 以 二氯甲烷 为溶剂， 反应 72.0h， 以70%的产率得到3-bromopropenyl acetate
  参考文献：
  名称：

  3-Bromopropenyl Esters in Organic Synthesis:  Indium- and Zinc-Mediated Entries to Alk-1-ene-3,4-diols

  摘要：

  Metallic indium and zinc readily add to 3-bromopropenyl acetate (5) and benzoate (6) either in THF or in water, affording the corresponding 3-acyloxyallyl organometallic compounds. Nucleophilic addition to aldehydes opens a route to alk-1-ene-3,4-diols 2 in good to excellent yields. Two synthetic protocols were developed, the former involving indium in THF under Grignard conditions and the latter involving zinc in aqueous ammonium chloride under Barbier conditions. The diastereoselectivity, under all the conditions examined, mainly depends on the nature of the carbonyl compound; conjugated aldehydes afford syn adducts 2, while unconjugated aldehydes display the opposite anti stereopreference.

  DOI：

  10.1021/jo0262457

文献信息

• Development of the Enantioselective Addition of Ethyl Diazoacetate to Aldehydes: Asymmetric Synthesis of 1,2-Diols
  作者：Barry M. Trost、Sushant Malhotra、Philipp Koschker、Pascal Ellerbrock

  DOI：10.1021/ja206995s

  日期：2012.2.1

  A novel synthetic strategy toward the asymmetric synthesis of vicinal diols bearing a tertiary center is presented. The method encompasses the dinuclear Mg-catalyzed asymmetric addition of ethyl diazoacetate into several aldehydes, oxidation of the diazo functionality, and diastereoselective alkyl transfer of various organometallics into the resulting chiral β-hydroxy-α-ketoesters to afford a diverse

  提出了一种新的合成策略，用于不对称合成带有三级中心的邻二醇。该方法包括双核 Mg 催化重氮乙酸乙酯不对称加成到几种醛中，重氮官能团的氧化，以及各种有机金属的非对映选择性烷基转移到所得的手性 β-羟基-α-酮酯中，以提供不同范围的 1,2 -高产率、非对映选择性和手性转移的二醇。
• Synthesis of pachastrissamine (jaspine B) and its derivatives by the late-stage introduction of the C-2 alkyl side-chains using olefin cross metathesis
  作者：Yuji Yoshimitsu、Jun Miyagaki、Shinya Oishi、Nobutaka Fujii、Hiroaki Ohno

  DOI：10.1016/j.tet.2013.03.091

  日期：2013.5

  An improved divergent synthesis of the four diastereomers of pachastrissamine from Garner's aldehyde has been reported. The common intermediate was synthesized by an indium-mediated acetoxyallylation reaction. The long alkyl side chain was introduced in the late stage of the synthesis using an olefin cross metathesis reaction. Biological evaluation of the chain modified analogs of the (2S,3S,4R)-isomer

  据报道，从加纳的醛中合成了四种帕斯帕司胺的非对映异构体的改进的发散性合成。常见的中间体是通过铟介导的乙酰氧基烯化反应合成的。在合成的后期，使用烯烃交叉复分解反应引入长烷基侧链。（2 S，3 S，4 R）-异构体的链修饰类似物的生物学评估表明，生物活性高度依赖于链长。
• Indium- and Zinc-Mediated Acyloxyallylation of Protected and Unprotected Aldotetroses—Revealing a Pronounced Diastereodivergence and a Fundamental Difference in the Performance of the Mediating Metal
  作者：Markus Draskovits、Christian Stanetty、Ian R. Baxendale、Marko D. Mihovilovic

  DOI：10.1021/acs.joc.7b03063

  日期：2018.3.2

  were successfully applied to the indium and also zinc-mediated acyloxyallylation, with the latter being a first for an unprotected sugar. The investigation largely benefited from the choice of these more exotic starting materials as it allowed unambiguous identification/quantification of the hexose-products which are available as authentic reference materials. The observed diastereoselectivities indicate

  十多年前，未经保护的醛糖的酰氧基化首次被证实为还原糖的潜在的优雅的二碳同系物（通过臭氧分解）。但是，它在实际案例合成中的应用仍然很少。在如此成功的展示之后，我们回答了有关这一有吸引力的转变的几个悬而未决的问题，我们进行了深入的方法学重新调查。将未受保护和受保护形式的差向异构体四聚体l-赤藓糖和d-苏糖成功应用于铟以及锌介导的酰氧基烯丙基化，后者是未保护糖的首创。该研究很大程度上得益于这些更具异国情调的起始原料的选择，因为它可以对己糖产品进行明确的鉴定/定量，而后者可作为可靠的参考材料。观察到的非对映选择性表明对底物有很强的控制作用（O2处的立体化学），并详细研究了试剂结构对选择性的影响。相关保护和未保护结构之间存在强烈的面部非对映差异，并且铟和锌之间的性能表现出乎意料的显着差异。
• Large-Scale Synthesis of Crystalline 1,2,3,4,6,7-Hexa-<i>O</i>-acetyl-<scp>L</scp>-<i>glycero-</i>α-<scp>D</scp>-<i>manno</i>-heptopyranose
  作者：Christian Stanetty、Ian R. Baxendale

  DOI：10.1002/ejoc.201500024

  日期：2015.4

  The higher-carbon sugar l-glycero-d-manno-heptose is a major constituent of the inner core region of the lipopolysaccharide (LPS) of many Gram-negative bacteria. All preparative routes used to date require multiple steps, and scalability has been rarely addressed. Here a highly practical synthesis of crystalline 1,2,3,4,6,7-hexa-O-acetyl-l-glycero-alpha-d-manno-heptopyranose by a simple four-step sequence

  高碳糖的l-甘油-d-甘露糖庚糖是许多革兰氏阴性细菌的脂多糖（LPS）的核心区域的主要组成部分。迄今为止，所有准备路线都需要多个步骤，而可扩展性很少得到解决。在此公开了一种高度实用的合成晶体1,2,3,4,6,7-六-O-乙酰基-1-甘油-α-d-甘露聚糖-七吡喃糖的简单方法，该方法是从l-lyxose开始的简单四步顺序进行的。仅需要两次重结晶，并且该过程以> 100 mmol的规模进行了证明，得到41 g的目标化合物。
• Reaction of Allylzinc Reagents and Zinc Enolates of Ketones with α-Amidoalkylphenyl Sulfones
  作者：Marino Petrini、Roberto Profeta、Paolo Righi

  DOI：10.1021/jo025606f

  日期：2002.6.1

  Alpha-amidoalkylphenyl sulfones behave as N-acylimino equivalents in the reaction with functionalized allylzinc reagents. The addition products obtained using the zinc derivative of ethyl 2-(bromomethyl)acrylate can be readily transformed into alpha-methylene-gamma-lactams using different cyclization procedures. The allylzinc reagent obtained from 3-bromo-1-acetoxy-1-propene directly affords protected

  α-酰胺基烷基苯基砜在与官能化烯丙基锌试剂的反应中表现为N-嘧啶基当量。使用2-（溴甲基）丙烯酸乙酯的锌衍生物获得的加成产物可以使用不同的环化方法容易地转化为α-亚甲基-γ-内酰胺。由3-溴-1-乙酰氧基-1-丙烯获得的烯丙基锌试剂直接提供受保护的1,2-氨基醇，优选使用抗立体异构体，而与所用α-酰胺基烷基苯基砜的结构无关。该程序可以扩展到使用从α-溴酮获得的烯醇锌，并导致合成N-保护的β-氨基酮。