(Z)-3-bromopropenyl acetate | 368421-69-6

• 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: (Z)-3-bromopropenyl acetate
• 英文别名: (Z)-1-acetoxy-3-bromo-1-propene；[(Z)-3-bromoprop-1-enyl] acetate
• CAS: 368421-69-6
• 化学式: C₅H₇BrO₂
• 分子量: 179.013
• InChiKey: JJPZBCGMCATWNR-RQOWECAXSA-N

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：

  2-甲基丙烯醛 、 (Z)-3-bromopropenyl acetate 在 indium 作用下， 以 四氢呋喃 为溶剂， 反应 8.0h， 生成 2-methyl-4-acetoxyhexa-1,5-dien-3-ol
  参考文献：
  名称：

  A New Protocol for the Acetoxyallylation of Aldehydes Mediated by Indium in THF

  摘要：

  [GRAPHICS]A new precursor of a formal 1-hydroxy allyl anion is represented by 3-bromo-1-acetoxy-1-propene, which is synthesized by the ZnCl2-catalyzed addition of acetyl bromide to propenal. 3-Bromo-1-acetoxy-1-propene reacts with indium powder in THF to give the corresponding 3-acetoxylated ally indium complex, which regioselectively adds to aldehydes, affording monoprotected 1-en-3,4-diols. Diastereoselectivity mainly depends on the nature of the aldehyde; saturated aldehydes afford anti adducts, whereas the alpha,beta -unsaturated aldehydes preferentially lead to the syn isomers.

  DOI：

  10.1021/ol016315g
• 作为产物：
  描述：

  乙酰溴 、 丙烯醛 在 zinc(II) chloride 作用下， 以 二氯甲烷 为溶剂， 以23.077%的产率得到
  参考文献：
  名称：

  通过铟介导的酰氧基化反应作为潜在相变材料合成高碳糖醇

  摘要：

  近年来，糖醇因其相对较高的储热密度（高达 350 J/g）而作为用于热能存储的有机相变材料 （PCM） 而受到广泛关注。在一项计算研究中，假设特定的高碳糖醇高达 ~ 450–500 J/g 的极高值。这些优化的结构具有主链中偶数个碳原子和立体化学构型，其中所有羟基都处于 1,3-反关系中，如天然 hexitol d-甘露醇中发现的那样。然而，这些甘露酸构型的高碳糖醇尚未作为 PCM 进行实验研究，所描述的合成路线是精心设计的多步合成。因此，我们的目标是用基于醛糖介导的酰氧烯丙基化 （IMA） 的简洁合成方案合成甘露醇系列的糖醇。在途中，C2-差向异构体很容易获得，即葡萄糖配置的糖醇，在次优的 1,3-syn-realtionship 中带有一组羟基。发现合成的化合物具有与预测值一致的热特性，并且发现具有八个碳原子的“完美”高碳糖醇确实具有出色的高熔化潜热 ~ 380 J/g，熔点为 260

  DOI：

  10.1007/s00706-023-03136-6

文献信息

• 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。
• 3-Bromozinc Propenyl Esters:  An Experimental and Theoretical Study of the Unique Stereocrossover Observed in Their Addition to Aromatic and Aliphatic Aldehydes
  作者：A. Bottoni、M. Lombardo、G. P. Miscione、J. B. Pujol Algué、C. Trombini

  DOI：10.1021/jo701661z

  日期：2008.1.1

  [GRAPHICS]We report the results of a combined experimental and theoretical study on the reaction of 3-bromopropenyl acetate in the presence of zinc with three different aldehydes (i.e., benzaldehyde, 2-methylpropanal, and cyclohexanecarboxaldehyde). A 80% de in favor of the anti product has been experimentally observed. with both saturated aldehydes, while for benzaldehyde, a 1:1 synlanti ratio has been found. DFT computations show the existence of three eta(1)-allylic organozinc complexes [gamma-(Z)-5a, gamma-(E)-5a, and alpha-5a], very close in energy. Only gamma-(Z)-5a and gamma-(E)-5a lead to the observed product. The computational investigation of the reaction of these allylic organozinc complexes with benzaldehyde and 2-methylpropanal demonstrates in both cases the existence of two competitive reaction paths leading to the syn and anti adducts, respectively. An anti preference has been found for 2-methylpropanal with both gamma-(Z)-5a and gamma-(E)-5a species (a diastereoselectivity larger than 80% is predicted), in agreement with the experiment. With benzaldehyde, while the reaction of gamma-(Z)-5a retains an anti-stereopreference (de = 70%), that involving gamma-(E)-5a is characterized by two degenerate transition states. In this case, the agreement between computations and experiments would be satisfactory under the assumption that the initial oxidative addition affords the gamma-(E)-5a zinc complex only. Additional MP2 computations have demonstrated that pi-stacking interactions can play a significant role in determining the relative energy of the transition states leading to the syn and anti products.
• ——
  作者：Marco Lombardo、Rugiada Girotti、Stefano Morganti、Claudio Trombini

  DOI：10.1039/b106759a

  日期：2001.11.7

  An exceptionally mild acetoxyallylation of aldehydes in water promoted by zinc is reported, using 3-bromo-1-acetoxyprop-1-ene as starting material; simple diastereoselectivity mainly depends on the nature of the aldehyde.