tert-butyl(E)-4-oxo-4-(2-oxo-1,3-oxazolidin-3-yl)-2-butenoate | 419532-01-7

• 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: tert-butyl(E)-4-oxo-4-(2-oxo-1,3-oxazolidin-3-yl)-2-butenoate
• 英文别名: tert-butyl (E)-4-oxo-4-(2-oxo-1,3-oxazolidin-3-yl)but-2-enoate
• CAS: 419532-01-7
• 化学式: C₁₁H₁₅NO₅
• 分子量: 241.244
• InChiKey: VXXXMRKOUWGCKF-SNAWJCMRSA-N

物化性质

• 沸点：
  315.8±44.0 °C(Predicted)
• 密度：
  1.238±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0.8
• 重原子数：
  17
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.55
• 拓扑面积：
  72.9
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  tert-butyl(E)-4-oxo-4-(2-oxo-1,3-oxazolidin-3-yl)-2-butenoate 在 N,N-二异丙基乙胺 sodium tetrahydroborate 、 4 A molecular sieve 、 水 、 magnesium triflimide 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 9.0h， 生成 (4S,5R)-1-(4-bromophenyl)-4,5-dihydro-5-hydroxymethyl-3-phenyl-1H-pyrazole-4-carboxylic acid tert-butyl ester
  参考文献：
  名称：

  An Entry to a Chiral Dihydropyrazole Scaffold:  Enantioselective [3 + 2] Cycloaddition of Nitrile Imines

  摘要：

  We have developed a versatile strategy to access dihydropyrazoles in highly enantioenriched form. Dipolar cycloaddition of electron-deficient acceptors and in situ-generated nitrile imines proceeds with high regio- and enantioselectivity using 10 mol % chiral Lewis acid catalyst. A variety of dihydropyrazoles that incorporate functionality for further manipulation have been prepared.

  DOI：

  10.1021/ja051650b
• 作为产物：
  描述：

  富马酸叔-丁酯 在 草酰氯 、 sodium hydride 、 N,N-二甲基甲酰胺 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 6.92h， 生成 tert-butyl(E)-4-oxo-4-(2-oxo-1,3-oxazolidin-3-yl)-2-butenoate
  参考文献：
  名称：

  An Entry to a Chiral Dihydropyrazole Scaffold:  Enantioselective [3 + 2] Cycloaddition of Nitrile Imines

  摘要：

  We have developed a versatile strategy to access dihydropyrazoles in highly enantioenriched form. Dipolar cycloaddition of electron-deficient acceptors and in situ-generated nitrile imines proceeds with high regio- and enantioselectivity using 10 mol % chiral Lewis acid catalyst. A variety of dihydropyrazoles that incorporate functionality for further manipulation have been prepared.

  DOI：

  10.1021/ja051650b

文献信息

• Acyclic Diastereoselection in Prochiral Radical Addition to Prochiral Olefins
  作者：Mukund P. Sibi、Tara R. Rheault、Sithamalli V. Chandramouli、Craig P. Jasperse

  DOI：10.1021/ja017510t

  日期：2002.3.1

  reactive halogenated radicals (6f,g) (>15:1 anti). Steric influence in alkyl radical additions was difficult to evaluate due to decreased reactivity when using bulky reaction partners; however, more reactive alpha-alkoxy radicals, it was found that increasing steric bulk leads to moderate increases in selectivity. In addition, higher selectivity was observed when employing lanthanide Lewis acids whose environment

  当前手性自由基添加到前手性受体时，立体化学偏好（syn 或 anti）具有重要意义。这项研究的主要重点是确定哪些因素会影响同时形成的 β 和 γ 手性中心之间的相对立体化学。虽然发现将烷基 (6a-d) 和 α-烷氧基自由基 (16a-c)（< 或 = 6:1 syn）添加到受体 4、7、8、10 和 14 具有中等的非对映选择性，但始终具有高选择性观察到活性较低的卤化自由基 (6f,g) (>15:1 anti)。由于使用庞大的反应伙伴时反应性降低，因此难以评估烷基自由基加成中的空间影响；然而，对于更具反应性的 α-烷氧基自由基，发现增加空间体积会导致选择性适度增加。此外，当使用镧系路易斯酸时观察到更高的选择性，其环境（反应性）使用非手性添加剂进行了改变，这表明在自由基反应中提高选择性是一种潜在的简单方法。总的来说，这些结果表明显着的立体电子效应对于在前手性受体上实现前手性自由基加成的高水平选择性是必要的。
• Tandem Radical Reactions and Ring-Closing Metathesis. Application in the Synthesis of Cyclooctenes
  作者：Mukund P. Sibi、Mona Aasmul、Hikaru Hasegawa、Thangaiah Subramanian

  DOI：10.1021/ol034924d

  日期：2003.8.1

  [reaction: see text] Fumarate- and acrylate-substituted oxazolidinones undergo tandem radical reaction to form dienes in moderate to good yields. The resulting dienes provide cyclooctenes in moderate to good yields after ring-closing metathesis (RCM). The role of the carbon backbone substituents and other variables in the efficiency of the eight-membered ring formation is discussed.

  [反应：见正文]富马酸酯和丙烯酸酯取代的恶唑烷酮进行串联自由基反应，以中等至良好的产率形成二烯。闭环易位（RCM）后，生成的二烯以中等到良好的产率提供环辛烯。讨论了碳骨架取代基和其他变量在八元环形成效率中的作用。
• An Efficient Method for Synthesis of Succinate-Based MMP Inhibitors
  作者：Mukund P. Sibi、Hikaru Hasegawa

  DOI：10.1021/ol026331t

  日期：2002.10.1

  [GRAPHICS]A differentially protected fumarate undergoes radical addition followed by allylstannane trapping to provide disubstituted succinates in good yields and high anti diastereoselectivity. The conversion of the succinate to a known MMP inhibitor has been accomplished.
• An Entry to a Chiral Dihydropyrazole Scaffold:  Enantioselective [3 + 2] Cycloaddition of Nitrile Imines
  作者：Mukund P. Sibi、Levi M. Stanley、Craig P. Jasperse

  DOI：10.1021/ja051650b

  日期：2005.6.1

  We have developed a versatile strategy to access dihydropyrazoles in highly enantioenriched form. Dipolar cycloaddition of electron-deficient acceptors and in situ-generated nitrile imines proceeds with high regio- and enantioselectivity using 10 mol % chiral Lewis acid catalyst. A variety of dihydropyrazoles that incorporate functionality for further manipulation have been prepared.