(3S,1’S)-3-[(1’-hydroxy-1’-(4’’-nitrophenyl))methyl]-tetrahydrothiopyran-4-one

• 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: (3S,1’S)-3-[(1’-hydroxy-1’-(4’’-nitrophenyl))methyl]-tetrahydrothiopyran-4-one
• 英文别名: (3S,1'R)-3-[(1'-hydroxy-1'-(4''-nitrophenyl))methyl]-tetrahydrothiopyran-4-one；3-(1-hydroxy-1-(4-nitrophenyl)methyl)-tetrahydrothiopyran-4-one；tetrahydro-3-[hydroxy(4-nitrophenyl)methyl]thiopyran-4-one；2-[hydroxy(p-nitrophenyl)methyl]tetrahydrothiopyran-4-one；(3S)-3-[(S)-hydroxy-(4-nitrophenyl)methyl]thian-4-one
• 化学式: C₁₂H₁₃NO₄S
• 分子量: 267.306
• InChiKey: HZWHUTNRBWDEOL-ZYHUDNBSSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.6
• 重原子数：
  18
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.42
• 拓扑面积：
  108
• 氢给体数：
  1
• 氢受体数：
  5

反应信息

• 作为产物：
  描述：

  对硝基苯甲醛 、 四氢噻喃-4-酮 在 sodium hydroxide 作用下， 生成 (3S,1’S)-3-[(1’-hydroxy-1’-(4’’-nitrophenyl))methyl]-tetrahydrothiopyran-4-one
  参考文献：
  名称：

  在离子液体中通过手性伯胺催化的不对称转移醛醇缩合反应 高度对映体合成环己酮的顺醛醇†

  摘要：

  手性伯叔二胺/三氟乙酸据发现，该化合物可有效催化离子液体中环己酮的外消旋顺式醇缩合物的动力学拆分，从而使手性顺式醇缩醛具有高达99：1的顺式/反式和99％的ee。

  DOI：

  10.1039/c0ob00682c

文献信息

• Proline-Catalyzed Ketone-Aldehyde Aldol Reactions are Accelerated by Water
  作者：Petri Pihko、Annika Nyberg、Annina Usano

  DOI：10.1055/s-2004-831296

  日期：——

  Proline-catalyzed aldol reactions between acetone or 4-thianone and different aldehydes are accelerated by addition of 1-10 equivalents of water to the reaction medium, allowing stoichiometric aldol reactions to proceed at acceptable rates.

  脯氨酸催化的丙酮或四氢噻吩-4-酮与不同醛之间的羟醛反应，通过向反应体系中添加1-10当量的水，可以加速反应进程，使得定量羟醛反应能够在可接受的速率下进行。
• Organocatalysis of asymmetric aldol reaction in water: comparison of catalytic properties of (S)-valine and (S)-proline amides
  作者：A. S. Kucherenko、D. E. Siyutkin、R. R. Dashkin、S. G. Zlotin

  DOI：10.1007/s11172-013-0132-z

  日期：2013.4

  (S)-Valine amides containing (S)- or (R)-α-phenylethyl substituents at N1 atom efficiently catalyze asymmetric aldol reactions between cyclic (heterocyclic) ketones and aromatic aldehydes in water, predominantly giving rise to the aldol anti-diastereomers in high yields (up to 98%) and enantiomeric excess (up to 94%).

  含有在N1原子上带有(S)-或(R)-α-苯乙基取代基的(S)-缬氨酰胺，能高效催化水中环状（杂环）酮与芳香醛的不对称Aldol反应，主要生成高产率（高达98%）和高对映体过量（高达94%）的Aldol反式异构体。
• (1R,2R)-Bis[(S)-prolinamido]cyclohexane Modified with Ionic Groups: The First C2-Symmetric Immobilized Organocatalyst for Asymmetric Aldol Reactions in Aqueous Media
  作者：Sergei V. Kochetkov、Alexandr S. Kucherenko、Sergei G. Zlotin

  DOI：10.1002/ejoc.201100707

  日期：2011.10

  The first C2-symmetric immobilized organocatalyst for asymmetric aldol reactions containing the (1R,2R)-bis[(S)-prolinamido]cyclohexane unit tagged with two imidazolium+/PF6– ion pairs has been synthesized. In its presence, (hetero)aromatic aldehydes reacted with linear or cyclic ketones in aqueous media to yield chiral aldols with high diastereo- and enantioselectivities and the catalyst could be

  已经合成了第一个用于不对称醛醇反应的 C2 对称固定化有机催化剂，该催化剂包含 (1R,2R)-双 [(S)-脯氨酰胺] 环己烷单元，并用两个咪唑鎓+/PF6- 离子对标记。在它的存在下，（杂）芳族醛与线性或环状酮在水性介质中反应以产生具有高非对映选择性和对映选择性的手性醛醇，并且催化剂可以回收和重复使用至少 10 次，而反应速率或选择性没有任何降低。
• Effect of additives on the proline-catalyzed ketone–aldehyde aldol reactions
  作者：Petri M. Pihko、Katri M. Laurikainen、Annina Usano、Annika I. Nyberg、Jatta A. Kaavi

  DOI：10.1016/j.tet.2005.09.070

  日期：2006.1

  The effect of bases, acids, and water as additives in proline-catalyzed ketone–aldehyde aldol reactions has been studied. While the reaction appears to be relatively tolerant to small amounts of tertiary amine bases or weak acids, it stops completely with strong acids. The use of water as an additive had a highly beneficial effect on reactions that were conducted with a stoichiometric ratio of ketone

  研究了碱，酸和水作为添加剂在脯氨酸催化的酮醛醛醇缩醛反应中的作用。尽管该反应似乎对少量的叔胺碱或弱酸具有相对的耐受性，但在强酸的作用下完全停止了。使用水作为添加剂对以酮与醛的化学计量比，特别是与环状酮进行的反应具有高度有益的效果。这允许在直接对映体选择性羟醛中有效地使用更珍贵的酮类如4-噻酮作为供体，并有助于纯化。
• Proline-catalyzed asymmetric aldol reactions of tetrahydro-4H-thiopyran-4-one with aldehydes
  作者：Dale E. Ward、Vishal Jheengut

  DOI：10.1016/j.tetlet.2004.09.061

  日期：2004.11

  Proline-catalyzed enantioselective direct intermolecular aldol reactions of tetrahydro-4H-thiopyran-4-one with various aldehydes give anti adducts with high diastereo- and enantioselectivities in moderate to excellent yields. With the aromatic aldehydes best results were obtained in wet DMF whereas dry DMSO generally was superior with the aliphatic aldehydes. Desulfurization of the adducts with Raney

  四氢-4 H-硫代吡喃-4-酮与各种醛的脯氨酸催化的对映选择性直接分子间羟醛缩合反应以中等至极好的收率得到具有高非对映体和对映体选择性的抗加合物。使用芳族醛，在湿DMF中可获得最佳结果，而干DMSO通常优于脂族醛。用阮内镍对加合物进行脱硫可提供与3-戊酮醛醇缩醛相当的产物，并可能在聚丙烯酸酯合成中得到应用。