Methyl 2-(p-methoxyphenyl)-5-(trichloromethyl)-trans-2-oxazoline-4-carboxylate

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: Methyl 2-(p-methoxyphenyl)-5-(trichloromethyl)-trans-2-oxazoline-4-carboxylate
• 英文别名: methyl (4R,5R)-2-(4-methoxyphenyl)-5-(trichloromethyl)-4,5-dihydro-1,3-oxazole-4-carboxylate
• 化学式: C₁₃H₁₂Cl₃NO₄
• 分子量: 352.602
• InChiKey: LZDOTTHESDHDEV-NXEZZACHSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.75
• 重原子数：
  21.0
• 可旋转键数：
  3.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.38
• 拓扑面积：
  57.12
• 氢给体数：
  0.0
• 氢受体数：
  5.0

反应信息

• 作为产物：
  描述：

  2-(p-methoxyphenyl)-5-methoxyoxazole 、 三氯乙醛 在 四氯化锡 作用下， 以 乙腈 为溶剂， 反应 45.0h， 以65%的产率得到Methyl 2-(p-methoxyphenyl)-5-(trichloromethyl)-trans-2-oxazoline-4-carboxylate
  参考文献：
  名称：

  Stereoselective synthesis of 2-oxazoline-4-carboxylates through Lewis acid-catalyzed formal [3+2] cycloadditions of 5-alkoxyoxazoles with aldehydes: catalytic effect of methylaluminum .beta.-binaphthoxide on cis-selectivity

  摘要：

  The formal [3 + 2] cycloadditions of 5-methoxy-2-(p-methoxyphenyl)oxazole with benzaldehyde, para- and meta-substituted benzaldehydes, propanal, cinnamaldehyde, and heterocyclic carboxaldehydes in the presence of methylaluminum beta-binaphthoxide gave the corresponding methyl 5-alkyl-2-(p-methoxyphenyl)-2-oxazoline-4-carboxylates with high cis-selectivity (up to 98%). The use of ortho-substituted benzaldehydes resulted in a decrease in the cis-selectivity. The reaction of 5-methoxy-2-(p-methoxyphenyl)oxazole with benzaldehyde in the presence of titanium(IV) chloride or tin(IV) chloride gave the corresponding trans-2-oxazoline-4-carboxylate with 85-86% trans-selectivity. The reaction of ethyl glyoxylate with 5-ethoxy-2-phenyloxazole catalyzed by a 1:1 mixture of titanium(IV) chloride and titanium tetraisopropoxide gave diethyl 2-phenyl-2-oxazoline-4,5-dicarboxylate with a preference for cis-selectivity (cis/trans = 84:6). The cis-selectivity of the reaction in the presence of methylaluminum beta-binaphthoxide can be explained by an antiperiplanar approach of the C4-C5 double bond of the oxazole to the aldehyde coordinated to the catalyst, followed by ring opening of the oxazole through a stepwise pathway involving zwitterionic intermediates.

  DOI：

  10.1021/jo00078a018

文献信息

• Suga Hiroyuki, Shi Xiaolan, Ibata Toshikazu, J. Org. Chem, 58 (1993) N 26, S 7397-7405
  作者：Suga Hiroyuki, Shi Xiaolan, Ibata Toshikazu

  DOI：——

  日期：——
• Stereoselective synthesis of 2-oxazoline-4-carboxylates through Lewis acid-catalyzed formal [3+2] cycloadditions of 5-alkoxyoxazoles with aldehydes: catalytic effect of methylaluminum .beta.-binaphthoxide on cis-selectivity
  作者：Hiroyuki Suga、Xiaolan Shi、Toshikazu Ibata

  DOI：10.1021/jo00078a018

  日期：1993.12

  The formal [3 + 2] cycloadditions of 5-methoxy-2-(p-methoxyphenyl)oxazole with benzaldehyde, para- and meta-substituted benzaldehydes, propanal, cinnamaldehyde, and heterocyclic carboxaldehydes in the presence of methylaluminum beta-binaphthoxide gave the corresponding methyl 5-alkyl-2-(p-methoxyphenyl)-2-oxazoline-4-carboxylates with high cis-selectivity (up to 98%). The use of ortho-substituted benzaldehydes resulted in a decrease in the cis-selectivity. The reaction of 5-methoxy-2-(p-methoxyphenyl)oxazole with benzaldehyde in the presence of titanium(IV) chloride or tin(IV) chloride gave the corresponding trans-2-oxazoline-4-carboxylate with 85-86% trans-selectivity. The reaction of ethyl glyoxylate with 5-ethoxy-2-phenyloxazole catalyzed by a 1:1 mixture of titanium(IV) chloride and titanium tetraisopropoxide gave diethyl 2-phenyl-2-oxazoline-4,5-dicarboxylate with a preference for cis-selectivity (cis/trans = 84:6). The cis-selectivity of the reaction in the presence of methylaluminum beta-binaphthoxide can be explained by an antiperiplanar approach of the C4-C5 double bond of the oxazole to the aldehyde coordinated to the catalyst, followed by ring opening of the oxazole through a stepwise pathway involving zwitterionic intermediates.