E-4-bromobut-2-enal dimethyl acetal | 66972-48-3

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: E-4-bromobut-2-enal dimethyl acetal
• 英文别名: (E)-4-bromo-1,1-dimethoxybut-2-ene；4-bromobut-2-enal dimethyl acetal
• CAS: 66972-48-3；18287-04-2
• 化学式: C₆H₁₁BrO₂
• 分子量: 195.056
• InChiKey: MOZFVZIBEWQCQW-ONEGZZNKSA-N

物化性质

• 沸点：
  202.3±40.0 °C(Predicted)
• 密度：
  1.322±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.1
• 重原子数：
  9
• 可旋转键数：
  4
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.67
• 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-4-bromobut-2-enal dimethyl acetal 在 sodium hydroxide 、 四丁基碘化铵 作用下， 以 四氢呋喃 、 水 为溶剂， 反应 0.25h， 以91%的产率得到bis-[1,1']-(4,4-dimethoxy)but-2-enyl ether
  参考文献：
  名称：

  Tandem Cycloadditions of Functionalized Bis-Dienes. An Orthogonal Route to New Dipseudoglycals

  摘要：

  A direct and stereocontrolled access to a new class of conjugated bis-dienes is presented that relies on a double conjugated-elimination reaction induced by the action of strong bases such as n-BuLi or KHMDS on bis-alpha,beta-unsaturated acetals. These bis-dienes undergo double [4 + 2] cycloadditions with activated dienophiles under thermal conditions. With methyl acrylate, the reaction is totally endo and regiocontrolled with respect to both dienes and exhibits up to 60% inter-ring diastereocontrol when performed under high pressure. Mixed adducts can also be obtained by adding successively two different dienophiles. Again, the endo and regiocontrols are total while the ring-to-ring diastereocontrol depends on reaction conditions but remain, most of the time, relatively low. Double hetero-Diels-Alder reactions have also been performed, yielding bicyclic skeletons of novel 4<->4' disaccharidic structures. Finally, the corresponding nonconjugated bis-dienes have also been evaluated in cycloadditions. They react at room temperature with NMM or diethyl ketomalonate to provide highly functionalized polycyclic structures in high yields.

  DOI：

  10.1021/jo990852l
• 作为产物：
  描述：

  1-(trimethylsiloxy)-1,3-butadiene 、 2,2-二甲氧基丙烷 在 N-溴代丁二酰亚胺(NBS) 作用下， 以 四氢呋喃 、 甲醇 为溶剂， 反应 1.5h， 生成 E-4-bromobut-2-enal dimethyl acetal
  参考文献：
  名称：

  乙炔取代基对炔烃分子内碳化反应的影响

  摘要：

  已经进行了一系列炔丙醚的分子内碳锂化，以评估末端取代基对环化效率和立体化学结果的影响。我们的结果表明，仅观察到 5-exo-dig 环化，并且仅获得了二氢苯并呋喃。根据末端取代基的性质，可以考虑两种情况。如果炔烃碳原子携带的末端取代基本身是碳原子，则只要末端炔丙基位置带有配位元素并且至少是二取代的，就可以发生环化。当环化发生时，它遵循反碳石化途径，从而导致环外双键的 E 异构体。仅在一种情况下(Ph)是回收的所得烯烃的E和Z异构体的混合物。如果调节环化条件，炔烃直接被 S 或 Si 取代，也可以发生环化。在三甲基甲硅烷基取代基的情况下，观察到顺式碳锂化。如果双键被恢复，在大多数情况下，在环外位置，产物可以直接芳构化为 SPh 取代的底物 24。此外，在后两种情况下，当进行乙烯基锂中间体的烷基化时，双键的异构化似乎是瞬间的。

  DOI：

  10.1002/ejoc.201101777

文献信息

• Conjugate-elimination on unsaturated acetals: A one-step route to functionalized 1,3-dienes.
  作者：Jacques Maddaluno、Odile Gaonac'h、Yann Le Gallic、Lucette Duhamel

  DOI：10.1016/0040-4039(95)01832-3

  日期：1995.11

  γ-Functionalized α,β-unsaturated dimethyl acelals undergo a methanol δ-elimination upon basic treatment, leading to 1,4-disubstituted 1,3-dienes in good yields and, in several cases, with high stereocontrol of the newly formed double bonds.

  γ-官能化的α，β-不饱和二甲基硬脂酸酯经过碱性处理后会被甲醇δ消除，从而以良好的收率得到1,4-二取代的1,3-二烯，在某些情况下，对新形成的双键具有高度的立体控制。
• 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.
• Desymmetrization of a <i>meso</i>-Allylic Acetal by Enantioselective Conjugate Elimination
  作者：Ling Xu、Thomas Regnier、Loïc Lemiègre、Pascal Cardinael、Jean-Claude Combret、Jean-Philippe Bouillon、Jérome Blanchet、Jacques Rouden、Anne Harrison-Marchand、Jacques Maddaluno

  DOI：10.1021/ol702877j

  日期：2008.3.1

  An unprecedented enantioselective deprotonation/conjugate elimination sequence, which transforms an allylic meso-dioxepane into a chiral diene, is described. The best desymmetrization conditions (ee up to 70%) involve s-BuLi and sparteine at -78 degrees C in THF.
• Trost, Barry M.; Dumas, Jacques; Villa, Marco, Journal of the American Chemical Society, 1992, vol. 114, # 25, p. 9836 - 9845
  作者：Trost, Barry M.、Dumas, Jacques、Villa, Marco

  DOI：——

  日期：——
• Unexpected behavior of dienol thio ethers gives versatile access to a large set of functionalized dienes
  作者：Odile Gaonac'h、Jacques Maddaluno、Joe Chauvin、Lucette Duhamel

  DOI：10.1021/jo00012a045

  日期：1991.6