(S)-4-hydroxyl-4-pyrid-2-ylbutan-2-one | 1015699-16-7

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡啶及其衍生物
• 英文名称: (S)-4-hydroxyl-4-pyrid-2-ylbutan-2-one
• 英文别名: 4-hydroxy-4-(pyridin-2-yl)butan-2-one；(4S)-4-hydroxy-4-pyridin-2-ylbutan-2-one
• CAS: 1015699-16-7
• 化学式: C₉H₁₁NO₂
• mdl: MFCD00634459
• 分子量: 165.192
• InChiKey: NYKHQRHPWDLZTL-VIFPVBQESA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -0.3
• 重原子数：
  12
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  50.2
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为产物：
  描述：

  吡啶-2-甲醛 、 丙酮 在 (4R)-[(15,19-dioxobeyeran-19-yl)oxy]-L-proline 作用下， 反应 12.0h， 生成 (R)-4-hydroxyl-4-pyrid-2-ylbutan-2-one 、 (S)-4-hydroxyl-4-pyrid-2-ylbutan-2-one
  参考文献：
  名称：

  简单的两亲异戊烯醇-脯氨酸偶联物作为手性催化剂，可在水存在下直接发生不对称醛醇缩合反应

  摘要：

  通过一锅法将异osteviol与l-脯氨酸缩合，合成了两种新型的两亲催化剂3和4。在仅1 mol％的负载量下，催化剂3在室温下于室温下对环己酮和取代的苯甲醛的直接羟醛反应显示出优异的活性（高达> 99％的收率）和立体选择性（高达99：1 dr，> 99％ee）。水的存在。此外，还研究了溶剂效应，催化剂负载量，底物范围，温度以及水对反应的影响。这些结果表明，在1-脯氨酸的4-位上具有手性凹和疏水取代基的催化剂为反应提供了高活性和立体选择性。

  DOI：

  10.1016/j.tetasy.2010.04.019

文献信息

• Tandem Catalysis by Lipase in a Vinyl Acetate-Mediated Cross-Aldol Reaction
  作者：Manjeet Kumar、Bhahwal A. Shah、Subhash C. Taneja

  DOI：10.1002/adsc.201000980

  日期：2011.5

  The lipase Novozym435 (0.6% w/w) was used in tandem with organocatalysts in a first vinyl/isopropenyl acetate‐mediated aldol reaction. The reaction was facilitated through the lipase‐catalyzed in situ generation of acetaldehyde/acetone. The important features of the present methodology include the mild and facile reaction conditions, regenerability of the lipase, comparatively high yields and minimal

  脂肪酶Novozym435（0.6％w / w）与乙酸乙烯酯/异丙烯基乙酸酯介导的醛醇缩合反应中的有机催化剂一起使用。该反应通过脂肪酶催化的乙醛/丙酮原位生成而得以促进。本方法的重要特征包括温和且容易的反应条件，脂肪酶的可再生性，相对高的收率和最小的副产物形成。
• Simple amphiphilic isosteviol–proline conjugates as chiral catalysts for the direct asymmetric aldol reaction in the presence of water
  作者：Ya-Jie An、Yun-Xiao Zhang、Ya Wu、Zhao-Min Liu、Chao Pi、Jing-Chao Tao

  DOI：10.1016/j.tetasy.2010.04.019

  日期：2010.4

  activity (up to >99% yield) and stereoselectivity (up to 99:1 dr, >99% ee) for the direct aldol reaction of cyclohexanone and substituted benzaldehydes at room temperature in the presence of water. In addition, solvent effects, catalyst loading, substrate scope, temperature, and the influence of water on the reactions were investigated. These results demonstrate that the catalysts with a chiral concave

  通过一锅法将异osteviol与l-脯氨酸缩合，合成了两种新型的两亲催化剂3和4。在仅1 mol％的负载量下，催化剂3在室温下于室温下对环己酮和取代的苯甲醛的直接羟醛反应显示出优异的活性（高达> 99％的收率）和立体选择性（高达99：1 dr，> 99％ee）。水的存在。此外，还研究了溶剂效应，催化剂负载量，底物范围，温度以及水对反应的影响。这些结果表明，在1-脯氨酸的4-位上具有手性凹和疏水取代基的催化剂为反应提供了高活性和立体选择性。
• Emergence of a catalytic tetrad during evolution of a highly active artificial aldolase
  作者：Richard Obexer、Alexei Godina、Xavier Garrabou、Peer R. E. Mittl、David Baker、Andrew D. Griffiths、Donald Hilvert

  DOI：10.1038/nchem.2596

  日期：2017.1

  artificial aldolase by an additional factor of 30 to give a >109 rate enhancement that rivals the efficiency of class I aldolases. The resulting enzyme catalyses a reversible aldol reaction with high stereoselectivity and tolerates a broad range of substrates. Biochemical and structural studies show that catalysis depends on a Lys-Tyr-Asn-Tyr tetrad that emerged adjacent to a computationally designed hydrophobic

  设计达到天然酶的速率和选择性的催化剂是蛋白质化学领域的长期目标。在这里，我们显示了基于超高通量液滴的微流体筛选平台可用于将先前优化的人工醛缩酶提高30倍，从而得到> 10 9速率提高，可与I类醛缩酶的效率相媲美。所得的酶以高的立体选择性催化可逆的羟醛反应，并耐受多种底物。生化和结构研究表明，催化作用取决于Lys-Tyr-Asn-Tyr四联体，该四联体在定向进化过程中与计算设计的疏水性囊袋相邻出现。这种残留物构图可以通过席夫碱形成激活底物，促进具有机械重要性的质子转移，并沿着复杂的反应坐标稳定多个过渡态。如此复杂的催化中心的出现表明，天然存在的酶的催化活性或机制，或产生这些酶的进化过程，没有什么神奇的。
• Dual stereocontrol in aldol reactions catalysed by hydroxyproline derivatives in the presence of a large amount of water
  作者：András A. Gurka、Kornél Szőri、Mihály Bartók、Gábor London

  DOI：10.1016/j.tetasy.2016.08.009

  日期：2016.10

  Parameters influencing dual stereocontrol in aldol reactions of water miscible acetone with aromatic aldehydes in the presence of a large amount of water using hydroxyproline based catalysts were studied. Stereocontrol was achieved by changing the acidity and basicity of the reaction media by the addition of achiral salts in the presence of a single chiral catalyst. Under acidic conditions (NH4Cl salt) the (R)-aldol product was formed in excess while basic aqueous media (carboxylate salts) led to the enrichment of the (S)-enantiomer. Reaction conditions under which the reaction is feasible were optimised and the effect of the structure of the hydroxyproline-based catalysts was investigated. The results show that the formation of a biphasic micellar system and the presence of an appropriate catalyst are both crucial for the reaction to occur. Although the catalyst structure influenced the formation and stabilisation of the micellar system to a large extent, its effect on the enantioselectivities were found to be less pronounced. (C) 2016 Elsevier Ltd. All rights reserved.
• Direct asymmetric aldol reactions catalyzed by l-proline-2,4,6-trinitroanilide
  作者：Kosuke Sato、Masami Kuriyama、Rumiko Shimazawa、Tsumoru Morimoto、Kiyomi Kakiuchi、Ryuichi Shirai

  DOI：10.1016/j.tetlet.2008.02.066

  日期：2008.4

  Direct aldol reactions of several aromatic aldehydes with ketones using L-proline-2,4,6-trinitroanilide catalyst 2d were conducted. Under optimized conditions, high enantioselectivity (99% ee), regioselectivity (up to 95:5), and diastereoselectivity (up to 98:2) were achieved. (C) 2008 Elsevier Ltd. All rights reserved.