(E/Z)-4-bromo-1,1-dimethoxy-3-methylbut-2-ene | 151018-39-2

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (E/Z)-4-bromo-1,1-dimethoxy-3-methylbut-2-ene
• 英文别名: 4-bromo-3-methylbut-2-enal dimethyl acetal；1,1-dimethoxy-3-methyl-4-bromobut-2-ene；4-bromo-1,1-dimethoxy-3-methylbut-2-ene
• CAS: 151018-39-2
• 化学式: C₇H₁₃BrO₂
• 分子量: 209.083
• InChiKey: NWXAXTQMYRQNKU-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.8
• 重原子数：
  10
• 可旋转键数：
  4
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.71
• 拓扑面积：
  18.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (E/Z)-4-bromo-1,1-dimethoxy-3-methylbut-2-ene 在 palladium on activated charcoal 哌啶 、 盐酸 、 4-二甲氨基吡啶 、 氢气 、 potassium carbonate 、 双三氟甲烷磺酰亚胺 、 溶剂黄146 、 sodium iodide 作用下， 以 四氢呋喃 、 甲醇 、 二氯甲烷 、 丙酮 、 甲苯 为溶剂， 生成 (+/-)-5-<4-(6-hydroxy-2,5,7,8-tetramethyl-2H-chromen-2-ylmethoxy)benzyl>thiazolidine-2,4-dione
  参考文献：
  名称：

  A short synthesis of troglitazone: An antidiabetic drug for treating insulin resistance

  摘要：

  Troglitazone was obtained in 5 steps from 4-bromo-1,1-dimethoxy-3-methylbut-2-ene with an overall yield of 7.5%. The formation of the chromane ring was achieved by condensing an unsaturated acetal with trimethylhydroquinone in the presence of bis(trifluoromethylsulfonyl)imide. (C) 1999 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0960-894x(99)00630-7
• 作为产物：
  描述：

  3-甲基-2-丁烯醛 在 溴 、 三乙胺 、 zinc(II) chloride 作用下， 以 乙醚 为溶剂， 反应 26.47h， 生成 (E/Z)-4-bromo-1,1-dimethoxy-3-methylbut-2-ene
  参考文献：
  名称：

  Unexpected behavior of dienol thio ethers gives versatile access to a large set of functionalized dienes

  摘要：

  DOI：

  10.1021/jo00012a045

文献信息

• Stereoselective Synthesis of (±)-α-Kainic Acid Using Free Radical Key Reactions
  作者：Mario D. Bachi、Nira Bar-Ner、Artem Melman

  DOI：10.1021/jo9607875

  日期：1996.1.1

  (1) except the C-2 acetic acid moiety. These intermediates were stereospecifically converted into (+/-)-alpha-kainic acid using a new method of temporary sulfur connection. Accordingly, CH(2)CO(2)Me is linked to the chiral isopropenyl anchor and then intramolecularly connected to the pyrrolidine ring and eventually disconnected from its anchor by a sequential reductive double elimination process in

  故意取代的丁烯基异氰酸酯12a的硫醇介导的自由基异构化，以及故意取代的丁烯基异硫氰酸酯22的n-Bu（3）SnH / AIBN介导的自由基环化作用分别得到（乙硫基）吡咯啉13a和硫代焦谷氨酸盐5和23。对这些杂环化合物进行还原，保护和脱保护，得到脯氨酸衍生物6和25，其中脯氨酸衍生物除具有C-2乙酸部分外，还包含α-海藻酸（1）的所有结构要素。 。使用新的临时硫连接方法将这些中间体立体定向转化为（+/-）-α-海藻酸。因此，
• Thermal/Hyperbaric Heterocycloaddition of 1,4-Dialkoxy-1,3-dienes:  The <i>de novo</i> (<i>E</i>,<i>Z</i>) Way to Sugars
  作者：Carole Bataille、Gautier Bégin、Anne Guillam、Loïc Lemiègre、Caroline Lys、Jacques Maddaluno、Loïc Toupet

  DOI：10.1021/jo0204193

  日期：2002.11.1

  1-(Z)-Alkoxy-4-(E)-methoxybutadiene derivatives have been reacted with ethylgyoxylate and diethyl ketomalonate under thermal or hyperbaric conditions. They provide, with a total regioselectivity and fair to total endoselectivities, the expected dihydropyranic cycloadducts. Three of those pseudoglycals have been converted in a few classical steps (deprotection, reduction, and dihydroxylation) into (racemic) allose, mannose, and gullose derivatives. The order of these three steps has a direct influence on the efficiency of the transformation and determines the stereochemistry of the final sugar.
• Synthesis and Cycloaddition Reactions of 1-(Arylthio)-1,3-dienes. A Combined Experimental and Theoretical Study of Bicyclic Adducts Structures
  作者：Jacques Maddaluno、Odile Gaonac'h、Albert Marcual、Loïc Toupet、Claude Giessner-Prettre

  DOI：10.1021/jo9519120

  日期：1996.1.1

  A method giving simple access to various 1-(phenylthio)-4-substituted-1,3-dienes (5-10) is described. The influence of the different functionalizations introduced on the dienic systems has been tested in a set of classical [4 + 2] cycloaddition reactions. Both the endo/exo and regio selectivities have been investigated. While the endo compound is, as expected, the only or major isomer in all cases, the regio competition between sulfur and oxygen is in favor of the oxygen substituent in the case studied here, in contrast to related works. For one type of adduct, X-ray crystallographic analysis and NMR spectroscopy have been used in conjunction with ab initio and semiempirical AM1 calculations to determine the structure and conformations of products as well as the energetic pathway from the primary concave endo cycloadduct (28) to a rearranged bicyclic structure (39), The theoretical results fully support the occurrence of a photochemical [1,3] sigmatropic shift of the thiophenyl group.
• Bromation des enamines du prénal et du crotonaldéhyde. Voie d'accès aux ω-bromo aldéhydes et ω-bromo acétals correspondants.
  作者：Lucette Duhamel、Jerôme Guillemont、Jean-Marie Poirier、Pierre Chabardes

  DOI：10.1016/s0040-4039(00)61186-3

  日期：1992.8

  Bromination of enamines of prenal and crotonaldehyde yields the corresponding omega-bromoaldehydes via the simple hydrolysis of iminium salts. The carbonyl function of these aldehydes can be protected as acetals or dioxolane. The overall process can be realized in a one pot procedure. The dioxolane is the starting material of a phosphonate which allows by condensation with beta-ionylidenacetaldehyde a direct access to the retinal with a 27.5% overall yield from the enamine 2
• A mild and direct oxidation of dienol thioethers into ketene dithioacetals.
  作者：Frank Freidanck、Jacques F. Maddaluno、Odile Gaonac'h、Lucette Duhamel

  DOI：10.1016/s0040-4039(00)79250-1

  日期：1993.6

  Functionalized dienol thioethers reacts with 3 eq. of thiophenol at room temperature in presence of dioxygen to give directly corresponding ketene dithioacetals in high yields.