(E)-methyl α-bromocrotonate

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 脂肪酰基
• 英文名称: (E)-methyl α-bromocrotonate
• 英文别名: (E)-α-bromocrotonate de methyle；methyl (E)-α-bromocrotonate；methyl (E)-2-bromobut-2-enoate；E-3-Methyl-2-bromacrylsaeure-methylester；methyl 2-bromobut-2-enoate；(e)-Methyl-2-bromobutenoate
• 化学式: C₅H₇BrO₂
• 分子量: 179.013
• InChiKey: DMKWWKUPZZAUQL-ONEGZZNKSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.8
• 重原子数：
  8
• 可旋转键数：
  2
• 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：

  (E)-methyl α-bromocrotonate 以 乙醇 为溶剂， 反应 2.0h， 生成 methyl (Z)-2-bromobut-2-enoate
  参考文献：
  名称：

  Hagiwara, Hisashiro; Abe, Futoshi; Uda, Hisashi, Journal of the Chemical Society. Perkin transactions I, 1993, # 21, p. 2651 - 2656

  摘要：

  DOI：
• 作为产物：
  描述：

  2,3-二溴丁酸甲酯 在 potassium carbonate 作用下， 以 正庚烷 、 乙腈 为溶剂， 生成 (E)-methyl α-bromocrotonate
  参考文献：
  名称：

  WO2006/99077

  摘要：

  公开号：

文献信息

• Towards the Sarpagine‐Ajmaline‐Macroline Family of Indole Alkaloids: Enantioselective Synthesis of an <i>N</i> ‐Demethyl Alstolactone Diastereomer
  作者：Dylan Dagoneau、Qian Wang、Jieping Zhu

  DOI：10.1002/chem.202000415

  日期：2020.4.9

  primary alcohol with acetoacetic acid followed by intramolecular Michael addition afforded the desired tetracycle with an excellent diastereoselectivity. Subsequent functional group manipulation and transannular cyclization of the amino alcohol afforded the N(1)-demethyl-3,5-diepi-alstolactone. We believe that the same synthetic route would afford the alstolactone should the amino alcohol with appropriate

  我们在这里报告了我们的策略，旨在使用功能化的四氢-6H-环辛基[b]吲哚-6-作为合成萜烯吲哚-大麦碱单萜吲哚生物碱的关键中间体。通过以下关键步骤合成了所需的三轮车：a）Evans的顺选择性醛醇缩合；b）使用3-氯丙酸的苯硫酚酯作为丙烯酸硫酯的代用品来合成2，3-二取代的吲哚，进行Liebeskind-Srogl交叉偶联。c）用于形成8元环的闭环易位（RCM）。计划将N-烯丙基化，然后进行分子内1,4-添加，以合成vobasine类天然产物。然而，在涉及阴离子，自由基和有机钯/有机基酮种类的多种条件下的环化未能产生桥环系统。另一方面，将侧基伯醇与乙酰乙酸酯化，然后分子内迈克尔加成，得到所需的四环具有非对映选择性。随后的官能团操纵和氨基醇的环过环化提供了N（1）-demethyl-3,5-diepi-alstolactone。我们认为，如果具有适当立体化学的氨基醇被用作起始原料，则相同的合成途径将提供戊内酯。
• α-Bromoacrylic Acids as C1 Insertion Units for Palladium-Catalyzed Decarboxylative Synthesis of Diverse Dibenzofulvenes
  作者：Minghao Zhang、Wenbo Deng、Mingjie Sun、Liwei Zhou、Guobo Deng、Yun Liang、Yuan Yang

  DOI：10.1021/acs.orglett.1c01888

  日期：2021.8.6

  Herein α-bromoacrylic acids have been employed as C1 insertion units to achieve the palladium-catalyzed [4 + 1] annulation of 2-iodobiphenyls, which provides an efficient platform for the construction of diverse dibenzofulvenes. This protocol enables the formation of double C(aryl)–C(vinyl) bonds via a C(vinyl)–Br bond cleavage and decarboxylation. It is particularly noteworthy that the method features

  在本文中，α-溴丙烯酸已被用作 C1 插入单元以实现钯催化的 2-碘联苯的 [4+1] 环化，这为构建各种二苯并富烯提供了一个有效的平台。该协议能够通过 C(乙烯基)-Br 键裂解和脱羧形成双 C(芳基)-C(乙烯基)键。特别值得注意的是，该方法具有广泛的底物范围，并且可以成功地将各种有趣的框架，如桥环、稠（杂）芳环和二乙烯基苯结合到产品中。
• Réactions de cyclopropanation par double addition de Michael.
  作者：Marc Joucla、Bernard Fouchet、Jacques Le Brun、Jack Hamelin

  DOI：10.1016/s0040-4039(00)98438-7

  日期：1985.1

  The addition of nucleophiles to alkyl α bromoacrylates in aprotic media leads to the stereospecific formation of cyclopropanes by a double Michael addition reaction.

  在非质子介质中将亲核试剂加到溴代丙烯酸烷基酯上可通过双迈克尔加成反应形成环丙烷的立体有规形成。
• Synthesis of a new family of 2-ethylidene-γ-unsaturated δ-amino esters via microwave activated Stille coupling
  作者：Gabriella Barozzino Consiglio、Francesca Gaggini、Alessandro Mordini、Gianna Reginato

  DOI：10.1007/s00726-009-0392-y

  日期：2010.6

  A simple approach to a new family of enantiomerically enriched polyunsaturated t-Boc-protected-delta-amino esters is described, via microwave promoted Stille coupling of (Z)-methyl-2-bromobutenoate with stannylated allylamines. The reaction conditions are mild and selective and disclose a simple way to 1-substituted butenoates of defined geometry.
• Enoate Reductase-Mediated Preparation of Methyl (<i>S</i>)-2-Bromobutanoate, a Useful Key Intermediate for the Synthesis of Chiral Active Pharmaceutical Ingredients
  作者：Elisabetta Brenna、Francesco G. Gatti、Alessia Manfredi、Daniela Monti、Fabio Parmeggiani

  DOI：10.1021/op200086t

  日期：2012.2.17

  Enoate reductases belonging to the Old Yellow Enzyme (OYE) family were employed to develop a biocatalysed approach to methyl (S)-2-bromobutanoate, a key intermediate for the introduction of a particular stereogenic unit into the molecular skeleton of a certain class of chiral drugs. Methyl (Z)-2-bromocrotonate afforded, respectively, (S)-2-bromobutanoic acid (ee = 97%) and methyl (S)-2-bromobutanoate (ee = 97%) by baker's yeast fermentation and by OYE1-3 biotransformations. The bioreductions of other methyl 2-haloalkenoates were also considered. It was observed that the (Z)- and (E)-diastereoisomers of alpha-bromo unsaturated esters afforded the same enantiomer of the corresponding reduced product.