(R)-3-((S)-hydroxy(4-nitrophenyl)methyl)dihydro-2H-thiopyran-4(3H)-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: (R)-3-((S)-hydroxy(4-nitrophenyl)methyl)dihydro-2H-thiopyran-4(3H)-one
• 英文别名: 3-(1-hydroxy-1-(4-nitrophenyl)methyl)-tetrahydrothiopyran-4-one；(3R)-3-[(S)-hydroxy-(4-nitrophenyl)methyl]thian-4-one
• 化学式: C₁₂H₁₃NO₄S
• 分子量: 267.306
• InChiKey: HZWHUTNRBWDEOL-CMPLNLGQSA-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：

  四氢噻喃-4-酮 、 对硝基苯甲醛 在 N-{(1S,2S)-2-[4-Me-C₆H₄CONH]-1,2-Ph₂-ethyl}-L-prolinamide 、 水 、 溶剂黄146 作用下， 以 四氢呋喃 为溶剂， 以91%的产率得到(R)-3-((S)-hydroxy(4-nitrophenyl)methyl)dihydro-2H-thiopyran-4(3H)-one
  参考文献：
  名称：

  立体和电子可调和双功能有机催化剂：环酮与醛的不对称羟醛反应的设计和应用

  摘要：

  在杂环酮的直接醛醇缩合反应中，已经开发并评估了可立体和电子可调的双功能有机催化剂。具有不同取代基的催化剂对类似的底物显示出不同的催化效率，表明微调两个NH基团中氢键强度的重要性。反应全部以良好至高收率进行，并且具有从90％至> 99％ee的优异对映选择性。在大多数情况下，抗羟醛加合物的非对映选择性高，为96/4至99/1。

  DOI：

  10.1021/jo0615089

文献信息

• Molecular-Sieves Controlled Diastereo- and Enantioselectivity: Unexpected Effect in the Organocatalyzed Direct Aldol Reaction
  作者：Jun-An Ma、Xiao-Juan Li、Guang-Wu Zhang、Lian Wang、Ming-Qing Hua

  DOI：10.1055/s-2008-1072586

  日期：2008.5

  An efficient asymmetric organocatalyst was developed for the direct aldol reaction between ketones and aldehydes to afford β-hydroxy ketones in high stereoselectivity (anti/syn up to 92:8, ee up to >99%). The key of the success was the use of activated molecular sieves (4 ŠMS), which acted as a water scavenger. The influence of additives such as water or different types of molecular sieves on the reactivity and stereoselectivity of the reaction was also studied.

  一种高效的非对称有机催化剂被开发出来，用于酮和醛之间的直接aldol反应，以高立体选择性（anti/syn高达92:8，ee高达>99%）制备β-羟基酮。成功的关键在于使用了活化的分子筛（4 Å MS），其作为水的清除剂。还研究了水分或不同类型分子筛等添加剂对反应活性和立体选择性的影响。
• Electrostatic Repulsion and Hydrogen-Bonding Interactions in a Simple<i>N</i>-Aryl-<scp>L</scp>-valinamide Organocatalyst Control the Stereoselectivity in Asymmetric Aldol Reactions
  作者：Yuya Tanimura、Kenji Yasunaga、Kaori Ishimaru

  DOI：10.1002/ejoc.201301138

  日期：2013.10

  A novel stereocontrol method for asymmetric aldol reactions of aldehydes with ketones is described. The stereoselectivity of the products is controlled by the electrostatic repulsion and hydrogen-bonding interactions of an N-aryl-L-valinamide catalyst. The use of this catalyst in a cross-aldol reaction allows easy access to bioactive 3-cyclohexanone-3-hydroxy-2-oxindole with excellent diastereo- (syn/anti

  描述了一种用于醛与酮的不对称羟醛反应的新型立体控制方法。产物的立体选择性受 N-芳基-L-缬氨酰胺催化剂的静电排斥和氢键相互作用控制。在交叉羟醛反应中使用该催化剂可以轻松获得具有优异非对映-（syn/anti = >99:1）和对映选择性（>99%ee）的生物活性 3-cyclohexone-3-hydroxy-2-oxindole。
• 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。
• Highly diastereo- and enantioselective direct Barbas–List aldol reactions promoted by novel benzamidoethyl and benzamidopropyl prolinamides in water
  作者：Rafael Pedrosa、José M. Andrés、Rubén Manzano、David Román、Silvia Téllez

  DOI：10.1039/c0ob00688b

  日期：——

  organocatalysts for enantioselective aldol reaction of aldehydes and cyclic ketones in water. In particular, prolinamide derived from achiral ethylene diamine was the best catalyst leading to anti aldols in excellent diastereomeric (up to 98/2) and enantiomeric (up to 99/1) ratios, thereby showing that lateral amide functionalities might be a key issue for facilitating “in water” chemistry. These catalysts

  制备了四种新型的苯甲酰胺基官能化的脯氨酰胺，并将其作为有机催化剂用于醛和环酮的对映体选择性醛醇缩合反应。 水。特别是，脯氨酰胺 衍生自非手性 乙烯二胺是导致抗羟醛的最佳催化剂，其非对映异构体（高达98/2）和对映异构体（高达99/1）的比例，从而表明侧酰胺功能可能是促进“对映体”的关键问题。水化学。这些催化剂比先前描述的那些便宜且易于制备。
• (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。