(S)-1-(4'-nitrophenyl)-1-hydroxy-3-hexanone

• 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: (S)-1-(4'-nitrophenyl)-1-hydroxy-3-hexanone
• 英文别名: 1-(4-nitrophenyl)-1-hydroxy-3-hexanone；1-hydroxy-1-(4-nitrophenyl)hexan-3-one；1(S)-hydroxy-1-(4-nitrophenyl)-3-hexanone；(1S)-1-hydroxy-1-(4-nitrophenyl)hexan-3-one
• 化学式: C₁₂H₁₅NO₄
• 分子量: 237.255
• InChiKey: QEGXDVYUEUIOCC-LBPRGKRZSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.4
• 重原子数：
  17
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.42
• 拓扑面积：
  83.1
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为产物：
  描述：

  1-(4'-硝基苯基)-1-羟基-5-甲氧基-3-戊酮 在 84G₃ aldolase antibody 作用下， 以 水 、 乙腈 为溶剂， 反应 3.0h， 生成 (S)-1-(4'-nitrophenyl)-1-hydroxy-3-hexanone
  参考文献：
  名称：

  Unusual reversal of regioselectivity in antibody-mediated aldol additions with unsymmetrical methyl ketones

  摘要：

  A catalytic regio- and enantioselective aldol reaction of various unsymmetrical methyl ketones with para-nitrobenzaldehyde has been developed using aldolase antibodies as the catalysts. It has been found that the sense and level of regioselectivity for the reactions catalysed by antibody 38C2 and 33F12 are highly dependent on the structure of both the donor and the acceptor but in contrast, antibodies 84G3 and 93F3 catalyse the exclusive formation of the linear regioisomer independent of the structure of the reactants examined. The level of enantiocontrol is very high for most reactions. Both linear aldol enantiomers could be accessed through aldol or retro-aldol reactions using the same antibody. Theoretical studies on regioisomeric alpha- and beta-heteroatom substituted enamines derived from unsymmetrical ketones suggest that most of the linear aldol products formed in the presence of antibodies 84G3 and 93F3 must be formed from intermediate enamines which are not the thermodynamically most favourable. (C) 2003 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2003.10.115

文献信息

• Substrate selective catalytic molecular hydrogels: the role of the hydrophobic effect
  作者：Cristina Berdugo、Juan F. Miravet、Beatriu Escuder

  DOI：10.1039/c3cc45623d

  日期：——

  A catalytic hydrogel is reported for the substrate selective direct aldol reaction of aliphatic ketones based on their hydrophobicity and on the emergence of catalytic activity only after self-assembly of the catalyst.

  据报道，基于疏水性选择性底物和催化剂自组装后催化活性出现的直接aldol反应，报道了一种用于脂肪族酮的催化水凝胶。
• A Simple Primary−Tertiary Diamine−Brønsted Acid Catalyst for Asymmetric Direct Aldol Reactions of Linear Aliphatic Ketones
  作者：Sanzhong Luo、Hui Xu、Jiuyuan Li、Long Zhang、Jin-Pei Cheng

  DOI：10.1021/ja069372j

  日期：2007.3.1

  regio- and diastereoselectivity and enantioselectivity under ambient temperature. Significantly, the reactions accommodate the synthetically important but challenging substrates, such as linear aliphatic ketones, with high regioselectivity and unprecedented syn diastereoselectivity. These results are in sharp contrast with the secondary amine mediated similar reactions wherein anti diastereoselectivity

  与已充分探索的带有仲胺的烯胺催化相比，开发高效的基于烯胺的伯胺催化剂直到最近仍然是一个难以捉摸的目标。我们在本文中提出了一种简单的手性伯-叔二胺 1d 与 TfOH 结合用作有效的基于烯胺的伯胺催化剂。1d-TfOH催化体系可以有效催化不对称直接醛醇反应，底物范围广，在环境温度下具有高区域选择性和非对映选择性以及对映选择性。值得注意的是，这些反应适应了合成上重要但具有挑战性的底物，例如线性脂肪族酮，具有高区域选择性和前所未有的顺式非对映选择性。
• Organo-catalyzed highly diastereo- and enantio-selective direct aldol reactions in water
  作者：Jun-Feng Zhao、Long He、Jun Jiang、Zhuo Tang、Lin-Feng Cun、Liu-Zhu Gong

  DOI：10.1016/j.tetlet.2008.03.131

  日期：2008.5

  The asymmetric direct aldol reactions of a wide scope of aromatic aldehydes, with unmodified ketones in the presence of 1 mol % of organocatalyst prepared from (2R,3R)-diethyl 2-amino-3-hydroxysuccinate and trans-4-hydroxy-l-proline, were performed in water, affording aldol products in high yields with excellent diastereoselectivities of up to >99:1 and enantioselectivities of up to 98%.

  在1 mol％由（2 R，3 R）-2-乙基-2-氨基-3-羟基琥珀酸二乙酯和反式-4-羟基-羟基乙酸制备的有机催化剂存在下，各种芳香醛与未改性的酮发生不对称直接羟醛反应l-脯氨酸在水中进行，以高收率提供羟醛产物，其非对映选择性高达> 99：1，对映选择性高达98％。
• A new (S)-prolinamide modified by an ionic liquid moiety—a high performance recoverable catalyst for asymmetric aldol reactions in aqueous media
  作者：Dmitry E. Siyutkin、Alexander S. Kucherenko、Sergei G. Zlotin

  DOI：10.1016/j.tet.2009.11.033

  日期：2010.1

  New prolinamide derivatives modified with ionic liquid moieties were synthesized and studied as organocatalysts in asymmetric aldol reactions in water. Aldol reactions between cycloalkanones or methylketones and aromatic aldehydes proceeded under studied conditions with high conversions (yields), diastereo- and enantioselectivities in the presence of a hydrophobic catalyst bearing a PF6 anion (1–5 mol %)

  合成了用离子液体部分改性的新的脯氨酰胺衍生物，并将其作为有机催化剂在水中不对称醛醇缩合反应中进行了研究。在具有PF 6阴离子（1-5摩尔％）的疏水催化剂的存在下，环烷酮或甲基酮与芳族醛之间的醛醇缩合反应在高转化率（产率），非对映和对映选择性的条件下进行。该方法是可扩展的，并且催化剂在至少四个反应循环中保持其非对映选择性和对映选择性，并在至少三个反应循环中保持其活性。
• (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。