(S)-N-[(1S,2R)-2-hydroxy-2,3-dihydro-1H-inden-1-yl]pyrrolidine-2-carbothioamide | 1126074-23-4

• 分子结构分类: 有机化合物 - 苯类化合物 - 茚满类
• 英文名称: (S)-N-[(1S,2R)-2-hydroxy-2,3-dihydro-1H-inden-1-yl]pyrrolidine-2-carbothioamide
• 英文别名: (2S)-N-[(1S,2R)-2-hydroxy-2,3-dihydro-1H-inden-1-yl]pyrrolidine-2-carbothioamide
• CAS: 1126074-23-4
• 化学式: C₁₄H₁₈N₂OS
• 分子量: 262.376
• InChiKey: GHTQORYVYFXGCA-XQQFMLRXSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.2
• 重原子数：
  18
• 可旋转键数：
  2
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  76.4
• 氢给体数：
  3
• 氢受体数：
  3

反应信息

• 作为产物：
  描述：

  (S)-tert-butyl 2-[(1S,2R)-2-(tert-butyldimethylsilyloxy)-2,3-dihydro-1H-inden-1-ylcarbamothioyl]pyrrolidine-1-carboxylate 在 盐酸 、 水 作用下， 以 1,4-二氧六环 为溶剂， 反应 0.5h， 以94%的产率得到(S)-N-[(1S,2R)-2-hydroxy-2,3-dihydro-1H-inden-1-yl]pyrrolidine-2-carbothioamide
  参考文献：
  名称：

  Prolinamides与脯氨酸硫酰胺在对映选择性无溶剂分子间和分子内羟醛反应中作为可回收的催化剂

  摘要：

  研究了可回收的L-脯氨酸酰胺和L-脯氨酸硫酰胺3催化的脂肪族酮与芳族醛的无溶剂不对称和直接的抗醛醇缩合反应。衍生自L-Pro和（R）-1-氨基茚满的L-脯氨酸硫代酰胺3d（5 mol％）是该方法最有效的催化剂，可提供高收率的抗醛醇加合物，并具有出色的非对映体和对映体选择性（up在0°C或室温下达到> 98/2 dr，最高可达98％ee）。脯氨酸硫酰胺3d是有效的有机催化剂，可用于首个不对称，无溶剂的分子内Hajos-Parrish-Eder-Sauer-Wiechert反应，其对映选择性（据报道高达88％ee）与有机溶剂中的对映选择性相当或更高。而且，有机催化剂3d可以通过简单的酸/碱萃取容易地回收和再利用。

  DOI：

  10.1002/adsc.200800430

文献信息

• Water<i>versus</i>Solvent-Free Conditions for the Enantioselective Inter- and Intramolecular Aldol Reaction Employing L-Prolinamides and L-Prolinethioamides as Organocatalysts
  作者：Diana Almaşi、Diego A. Alonso、Andrea-Nekane Balaguer、Carmen Nájera

  DOI：10.1002/adsc.200800814

  日期：2009.5

  Abstractmagnified imageOrganocatalysts 1, derived from L‐proline and (1S,2R)‐cis‐1‐aminoindan‐2‐ol or (R)‐1‐aminoindane, are evaluated as promoters in the direct asymmetric aldol reaction between ketones and aromatic aldehydes in the presence of water and under solvent‐free reaction conditions. L‐Prolinethioamides 1c and 1d exhibited higher enantioselectivity than the corresponding prolinamides 1a and 1b in the model aldol reaction between cyclohexanone and 4‐nitrobenzaldehyde in the presence of 4‐nitrobenzoic acid as cocatalyst. In particular, L‐prolinethioamide 1d (5 mol%), derived from L‐proline and (R)‐1‐aminoindane, is shown as the most efficient organocatalyst studied promoting the direct aldol reaction of cycloalkyl, alkyl, and α‐functionalized ketones with aromatic aldehydes in the presence of water and under solvent‐free reaction conditions employing only 2 equivalents of nucleophile. Generally, anti‐aldol products are obtained in high yields and excellent diastereo‐ and enantioselectivities (up to >98/2 anti/syn, up to 98% ee). Solvent‐free conditions give slightly higher dr and ee than using water as solvent. In addition, organocatalyst 1d can be easily recovered by extractive work‐up and reused. Prolinethioamide 1d (5 mol%) in combination with 4‐NO2C6H4CO2H (5 mol%) is also a very effective organocatalytic system for the asymmetric solvent‐free intramolecular Hajos–Parrish–Eder–Sauer–Wiechert reaction with comparable or higher levels of enantioselectivity (up to 88% ee) to other reported catalysts in organic solvents.