(1'S,2E)-pentafluorophenyl 3-[5-(tert-butyl)oxycarbonyl-4,4-dimethyl-3,5-oxazolidinyl]prop-2-enoate | 167281-01-8

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯酚酯
• 英文名称: (1'S,2E)-pentafluorophenyl 3-[5-(tert-butyl)oxycarbonyl-4,4-dimethyl-3,5-oxazolidinyl]prop-2-enoate
• 英文别名: tert-butyl (4S)-2,2-dimethyl-4-[(E)-3-oxo-3-(2,3,4,5,6-pentafluorophenoxy)prop-1-enyl]-1,3-oxazolidine-3-carboxylate
• CAS: 167281-01-8
• 化学式: C₁₉H₂₀F₅NO₅
• 分子量: 437.364
• InChiKey: NAWJBOKWTSQUMP-UCUJLANTSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.7
• 重原子数：
  30
• 可旋转键数：
  6
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.47
• 拓扑面积：
  65.1
• 氢给体数：
  0
• 氢受体数：
  10

反应信息

• 作为反应物：
  描述：

  (1'S,2E)-pentafluorophenyl 3-[5-(tert-butyl)oxycarbonyl-4,4-dimethyl-3,5-oxazolidinyl]prop-2-enoate 在 4-甲基苯磺酸吡啶 作用下， 以 四氢呋喃 、 甲醇 、 乙醚 、 甲苯 为溶剂， 反应 93.5h， 生成 tert-butyl N-[(4S,4aR,8aR)-6-methylidene-1-oxo-4,4a,5,7,8,8a-hexahydro-3H-isochromen-4-yl]carbamate
  参考文献：
  名称：

  Internal activation of acrylate-type dienophiles for the Diels-Alder reaction. Stereoselective synthesis of conformationally constrained glutamate analogs

  摘要：

  The [4+2] cycloaddition reaction of the unreactive acrylate-type dienophiles such as 5a and 6a was accomplished by introducing an electronegative or electron-withdrawing group as the ester counterpart. Among them, the pentafluorophenyl (PFP) group was found to be an excellent ester counterpart in view of its rate acceleration and chemical stability under the reaction conditions. The C-13 NMR spectral data of the dienophiles with the PFP group suggested that the conjugated CC-double bond was strongly polarized. The internal activation was found to be effective for the related dienophile or other dienes, in particular, unstable to Lewis acid catalysts. A successful application of this method is demonstrated by the syntheses of conformationally restricted analogs of L-glutamate, 3 and 4. (C) 1998 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4020(98)00219-1
• 作为产物：
  描述：

  (4S)-1,1-Dimethylethyl 4-<(E)-3'-methoxy-3'-oxo-1'-propenyl>-2,2-dimethyl-3-oxazolidinecarboxylate 在 4-二甲氨基吡啶 、 sodium hydroxide 、 盐酸-N-乙基-Nˊ-(3-二甲氨基丙基)碳二亚胺 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 21.0h， 生成 (1'S,2E)-pentafluorophenyl 3-[5-(tert-butyl)oxycarbonyl-4,4-dimethyl-3,5-oxazolidinyl]prop-2-enoate
  参考文献：
  名称：

  Internal activation of acrylate-type dienophiles for the Diels-Alder reaction. Stereoselective synthesis of conformationally constrained glutamate analogs

  摘要：

  The [4+2] cycloaddition reaction of the unreactive acrylate-type dienophiles such as 5a and 6a was accomplished by introducing an electronegative or electron-withdrawing group as the ester counterpart. Among them, the pentafluorophenyl (PFP) group was found to be an excellent ester counterpart in view of its rate acceleration and chemical stability under the reaction conditions. The C-13 NMR spectral data of the dienophiles with the PFP group suggested that the conjugated CC-double bond was strongly polarized. The internal activation was found to be effective for the related dienophile or other dienes, in particular, unstable to Lewis acid catalysts. A successful application of this method is demonstrated by the syntheses of conformationally restricted analogs of L-glutamate, 3 and 4. (C) 1998 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4020(98)00219-1

文献信息

• Internal activation of acrylate-type dienophiles in Diels-Alder reactions
  作者：Toshiyuki Kan、Yasufumi Ohfune

  DOI：10.1016/0040-4039(94)02379-p

  日期：1995.2

  Diels-Alder reactions of less reactive acrylate-type dienophiles with dienes were achieved by replacing its ester counterpart to a pentafluorophenyl group, which remarkably enhanced the reactivity of the dienophiles to give the corresponding cycloadducts in excellent yields with a high stereoselectivity.