(E)-N-methoxy-N-methyl-4-oxopent-2-enamide | 455253-15-3

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (E)-N-methoxy-N-methyl-4-oxopent-2-enamide
• CAS: 455253-15-3
• 化学式: C₇H₁₁NO₃
• 分子量: 157.169
• InChiKey: UVUJYGQXQSGXRV-SNAWJCMRSA-N

物化性质

• 沸点：
  214.6±42.0 °C(Predicted)
• 密度：
  1.079±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  -0.3
• 重原子数：
  11
• 可旋转键数：
  3
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.43
• 拓扑面积：
  46.6
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (E)-N-methoxy-N-methyl-4-oxopent-2-enamide 在 2,6-二甲基吡啶 、 硼烷四氢呋喃络合物 、 叔丁基锂 、 sodium methylate 、 二甲基氯化铝 、 二异丁基氢化铝 、 对甲苯磺酸 、 pyridinium chlorochromate 作用下， 以 四氢呋喃 、 甲醇 、 乙醚 、 正己烷 、 二氯甲烷 、 正戊烷 、 苯 为溶剂， 反应 38.83h， 生成 (±)-(4R,4aR,7S,9S,9aR)-9-((tert-butyldimethylsilyl)oxy)-4-methylhexahydro-1H-spiro[4a,7-epoxybenzo[7]annulene-2,2'-[1,3]dioxolan]-6(5H)-one
  参考文献：
  名称：

  Synthesis of the Tricyclic Ring Structure of Daphnanes via Intramolecular [4 + 3] Cycloaddition/SmI₂-Pinacol Coupling

  摘要：

  A synthetic approach toward the tricyclic 5,7,6-membered ring structure Of daphnane-family natural products is described. An intramolecular [4 + 3] cycloaddition reaction of furan with an oxypentadienyl cation constructed the oxa-bridged bicyclic structure in a stereoselective fashion. Structural analysis revealed that the desired exo isomer was predominantly acquired through epimerization. Finally, formation of the five-membered ring was achieved through SmI2-mediated pinacol coupling.

  DOI：

  10.1021/acs.orglett.5b01054
• 作为产物：
  描述：

  N-甲氧基-N-甲基-2-(三苯基磷)乙酰胺N-甲氧基-N-甲基-2-(三苯基磷)乙酰胺 、 羟基丙酮 在 manganese(IV) oxide 作用下， 以 二氯甲烷 为溶剂， 反应 1.0h， 以100%的产率得到(E)-N-methoxy-N-methyl-4-oxopent-2-enamide
  参考文献：
  名称：

  The in situ oxidation–Wittig reaction of α-hydroxyketones

  摘要：

  原位氧化-维蒂希法已被应用于α-羟基酮，避免了通常与α-酮醛相关的问题；该程序非常简单，在许多情况下能够获得高产率的产物γ-酮基克酮酸酯；该程序还成功地应用于乙基甘醇酸盐和甘醛二聚体。

  DOI：

  10.1039/b201513g

文献信息

• Highly Selective Rhodium-Catalyzed Conjugate Addition Reactions of 4-Oxobutenamides
  作者：Jamie L. Zigterman、Jacqueline C. S. Woo、Shawn D. Walker、Jason S. Tedrow、Christopher J. Borths、Emilio E. Bunel、Margaret M. Faul

  DOI：10.1021/jo701682c

  日期：2007.11.1

  [GRAPHICS]A variety of 4-oxobutenamides 1 were subjected to rhodium-catalyzed conjugate addition with arylboronic acids providing high regio- and enantioselectivity (97:3 to > 99:1, > 96% ee) and moderate to excellent yields (54-99%). The key to high selectivity is the use of sterically demanding P-chiral diphosphines, such as Tangphos or Duanphos. The product oxobutanamides 2 may be converted to alternate targets by selective derivatization of either the amide or ketone functional group. A stereochemical model predicting the absolute sense of induction was developed based on single-crystal X-ray structures of product and precatalyst.
• Synthesis of the Tricyclic Ring Structure of Daphnanes via Intramolecular [4 + 3] Cycloaddition/SmI₂-Pinacol Coupling
  作者：Ahmed H. E. Hassan、Jae Kyun Lee、Ae Nim Pae、Sun-Joon Min、Yong Seo Cho

  DOI：10.1021/acs.orglett.5b01054

  日期：2015.6.5

  A synthetic approach toward the tricyclic 5,7,6-membered ring structure Of daphnane-family natural products is described. An intramolecular [4 + 3] cycloaddition reaction of furan with an oxypentadienyl cation constructed the oxa-bridged bicyclic structure in a stereoselective fashion. Structural analysis revealed that the desired exo isomer was predominantly acquired through epimerization. Finally, formation of the five-membered ring was achieved through SmI2-mediated pinacol coupling.
• The in situ oxidation–Wittig reaction of α-hydroxyketones
  作者：Karen A. Runcie、Richard J. K. Taylor

  DOI：10.1039/b201513g

  日期：2002.4.19

  In situ oxidation–Wittig methodology has been applied to α-hydroxyketones avoiding the problems normally associated with α-ketoaldehydes; the procedure is practically simple, and in many cases gives high yields of the product γ-ketocrotonates; the procedure has also been successfully utilised with ethyl glycolate and glycolaldehyde dimer.

  原位氧化-维蒂希法已被应用于α-羟基酮，避免了通常与α-酮醛相关的问题；该程序非常简单，在许多情况下能够获得高产率的产物γ-酮基克酮酸酯；该程序还成功地应用于乙基甘醇酸盐和甘醛二聚体。