ethyl 2-(4-nitro-5-(thiophen-2-yl)-1-tosylpyrrolidin-3-yl)-acetate | 1369894-05-2

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: ethyl 2-(4-nitro-5-(thiophen-2-yl)-1-tosylpyrrolidin-3-yl)-acetate
• 英文别名: ethyl 2-[(3S,4R,5R)-1-(4-methylphenyl)sulfonyl-4-nitro-5-thiophen-2-ylpyrrolidin-3-yl]acetate
• CAS: 1369894-05-2
• 化学式: C₁₉H₂₂N₂O₆S₂
• 分子量: 438.525
• InChiKey: VLIRBOUDNNLRNB-KYNGSXCRSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.7
• 重原子数：
  29
• 可旋转键数：
  7
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.42
• 拓扑面积：
  146
• 氢给体数：
  0
• 氢受体数：
  8

反应信息

• 作为产物：
  描述：

  4-溴巴豆酸乙酯 在 N-[3,5-二(三氟甲基)苯基]-N-[(9R)-6-甲氧基-9-二奎宁基]硫脲 、 potassium carbonate 、 三氟乙酸 、 sodium iodide 作用下， 以 二氯甲烷 、 N,N-二甲基甲酰胺 、 甲苯 为溶剂， 反应 8.0h， 生成 ethyl 2-(4-nitro-5-(thiophen-2-yl)-1-tosylpyrrolidin-3-yl)-acetate 、 ethyl 2-(4-nitro-5-(thiophen-2-yl)-1-tosylpyrrolidin-3-yl)-acetate 、 ethyl 2-(4-nitro-5-(thiophen-2-yl)-1-tosylpyrrolidin-3-yl)-acetate
  参考文献：
  名称：

  Organocatalytic asymmetric synthesis of trisubstituted pyrrolidines via a cascade reaction

  摘要：

  A new bifunctional thiourea II catalyzed methodology was developed for the synthesis of chiral trisubstituted pyrrolidines using 4-aminocrotonate 1a/1b and nitroolefins 2a-g as starting materials. Two different N-protected 4-aminocrotonates la and 1b were tested for the reaction with la giving the desired product 3a with a high diastereomeric ratio (>20:1) but with low enantioselectivity (ee up to 7%). N-Tosyl-4-aminocrotonate 1b, however, yielded the product with moderate dr (up to 68:32) but with high ee in the case of the major trans-trans-isomers 4a-g (ee from 92% to 98%) and modest enantiomeric excess for the minor trans-cis-isomers 4a'-g' (ee up to 57%). This methodology was also successfully applied when (E)-beta-methyl-trans-beta-nitrostyrene 2h was used as the starting nitroalkene to provide the product with dr 70/30 and with ee of 63% and 67%, respectively. The absolute configuration of both isomers was established using chiral derivatization with Mosher's and mandelic acids, with the relative stereochemistry being determined via NMR analysis. (C) 2012 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetasy.2012.01.021

文献信息

• Organocatalytic asymmetric synthesis of trisubstituted pyrrolidines via a cascade reaction
  作者：Artur Noole、Tõnis Pehk、Ivar Järving、Margus Lopp、Tõnis Kanger

  DOI：10.1016/j.tetasy.2012.01.021

  日期：2012.1

  A new bifunctional thiourea II catalyzed methodology was developed for the synthesis of chiral trisubstituted pyrrolidines using 4-aminocrotonate 1a/1b and nitroolefins 2a-g as starting materials. Two different N-protected 4-aminocrotonates la and 1b were tested for the reaction with la giving the desired product 3a with a high diastereomeric ratio (>20:1) but with low enantioselectivity (ee up to 7%). N-Tosyl-4-aminocrotonate 1b, however, yielded the product with moderate dr (up to 68:32) but with high ee in the case of the major trans-trans-isomers 4a-g (ee from 92% to 98%) and modest enantiomeric excess for the minor trans-cis-isomers 4a'-g' (ee up to 57%). This methodology was also successfully applied when (E)-beta-methyl-trans-beta-nitrostyrene 2h was used as the starting nitroalkene to provide the product with dr 70/30 and with ee of 63% and 67%, respectively. The absolute configuration of both isomers was established using chiral derivatization with Mosher's and mandelic acids, with the relative stereochemistry being determined via NMR analysis. (C) 2012 Elsevier Ltd. All rights reserved.