2-(hydroxyl(4-chlorophenyl)methyl)cyclopentanone | 1121715-25-0

• 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: 2-(hydroxyl(4-chlorophenyl)methyl)cyclopentanone
• 英文别名: (S)-2-((R)-(4-chlorophenyl)(hydroxy)methyl)cyclopentanone；2-[hydroxy-(4-chloro-phenyl)methyl]-cyclopentanone；(S)-2-((R)-hydroxy(4-chlorophenyl)methyl)cyclopentan-1-one；(2S)-2-[(R)-hydroxy(4-chlorophenyl)methyl]cyclopentan-1-one；(S)-2-((R)-hydroxyl(4-chlorophenyl)methyl)-cyclopentan-1-one；(2S)-2-[(R)-(4-chlorophenyl)-hydroxymethyl]cyclopentan-1-one
• CAS: 1121715-25-0
• 化学式: C₁₂H₁₃ClO₂
• 分子量: 224.687
• InChiKey: XJEXURBWZPVDPC-PWSUYJOCSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.5
• 重原子数：
  15
• 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：
  37.3
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为产物：
  描述：

  4-氯苯甲醛 、 环戊酮 在 tris(1-glycyl-3-methyl imidazolium chloride-iron(III)) 作用下， 以 neat (no solvent) 为溶剂， 反应 12.0h， 以93%的产率得到
  参考文献：
  名称：

  Development of highly enantioselective asymmetric aldol reaction catalyzed by 1-glycyl-3-methyl imidazolium chloride–iron(III) complex

  摘要：

  A novel, effective asymmetric 1-glycyl-3-methyl imidazolium chloride-iron(III) [[Gmim]Cl-Fe(III)] complex was synthesized and studied as organocatalyst in asymmetric aldol addition under solvent free condition at 25 degrees C. The hydrophobic group of amino acid favors reagent diffusion toward the chloroglycine moiety increasing the catalytic activity of supported iron complex. This method contains simplified product isolation and catalyst recycling, affording substituted aromatic aldehydes imparting high yield of aldol with excellent stereo-selectivity. This recyclable heterogeneous catalyst provides a simple strategy for the generation of a variety of new C-C bonds under environmentally benign condition. (C) 2013 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.molcata.2013.08.029

文献信息

• Organocatalysis with cysteine derivatives: recoverable and cheap chiral catalyst for direct aldol reactions
  作者：Shi Li、Xiangkai Fu、Chuanlong Wu

  DOI：10.1007/s11164-011-0336-5

  日期：2012.1

  Highly enantioselective, recoverable and cheap cysteine derivatives have been developed with improved solubility properties in common, nonpolar organic solvents. The reactions were catalyzed using 5 mol% 1e, and the aldol products could be obtained with up to 99:1 syn/anti ratio and >99% ee. The catalyst could be easily recovered and reused, with only a slight decrease of enantioselectivity observed for five cycles. Catalyst 1e can be efficiently used in large-scale reactions with enantioselectivity being maintained at the same level, which offers great possibility for application in industry. (i) Direct aldol reactions proceeded in 1,2-dichloroethane using simple procedures. (ii) Direct S-acylation of cysteine to give organocatalysts 1a–f can be economically carried out easily in a single step from commercially available sources, with both enantiomers being readily available. (iii) 5 mol% catalyst 1e was sufficient to furnish the aldol products in excellent yields (up to 93%) and enantioselectivities (up to 99%). (iv) Catalyst 1e could be easily recovered and reused, and also can be efficiently used in large-scale reactions with enantioselectivity being maintained at the same level, which offers great possibility for applications in industry.

  开发了一种高度对映选择性、可回收且廉价的半胱氨酸衍生物，其在常见的非极性有机溶剂中具有改善的溶解性特性。反应使用5 mol%催化剂1e进行催化，醛醇产物的syn/anti比率可高达99:1，对映体过量（ee）超过99%。催化剂可以轻松回收并重复使用，经过五个循环后仅观察到轻微的对映选择性降低。催化剂1e可以在大规模反应中有效使用，并维持相同水平的对映选择性，这为其在工业中的应用提供了很大可能性。(i) 直接醛醇反应在1,2-二氯乙烷中通过简单的程序进行。(ii) 半胱氨酸的直接S-酰化以获得有机催化剂1a-f，可以轻松地从商业来源通过一步经济地进行，两种对映体均易于获得。(iii) 5 mol%催化剂1e足以以优异的产率（高达93%）和对映选择性（高达99%）提供醛醇产物。(iv) 催化剂1e可以轻松回收和重复使用，并且可以在大规模反应中有效使用，保持相同水平的对映选择性，这为其在工业中的应用提供了极大的可能性。
• Intramolecular hydrogen bonding guides a cationic amphiphilic organocatalyst to highly stereoselective aldol reactions in water
  作者：Ángel M. Valdivielso、Alba Catot、Ignacio Alfonso、Ciril Jimeno

  DOI：10.1039/c5ra12135c

  日期：——

  A novel amphiphilic guanidine organocatalyst, efficient for asymmetric aldol reactions of ketones in water at neutral pH, is disclosed. The reaction presented a clear substrate dependence depicting a free energy linear correlation with ee. Intramolecular hydrogen bonding in the acylguanidine moiety was identified as the key structural motif.

  公开了一种新颖的两亲胍有机催化剂，其对于在中性pH下的水中的酮的不对称醛醇缩合反应是有效的。该反应呈现出清晰的底物依赖性，其描绘了与ee的自由能线性相关性。酰基胍部分中的分子内氢键被鉴定为关键的结构基序。
• New Simple Hydrophobic Proline Derivatives as Highly Active and Stereoselective Catalysts for the Direct Asymmetric Aldol Reaction in Aqueous Medium
  作者：Francesco Giacalone、Michelangelo Gruttadauria、Paolo Lo Meo、Serena Riela、Renato Noto

  DOI：10.1002/adsc.200800555

  日期：——

  different hydrophobic properties of the acyl group were easily synthesized and used as catalysts in the direct asymmetric aldol reaction between cyclic ketones (cyclohexanone and cyclopentanone) and several substituted benzaldehydes. Reactions were carried out using water, this being the best reaction medium examined. Screening of these catalysts showed that compounds bearing the most hydrophobic acyl

  容易合成具有不同疏水性的酰基的新的4-取代的酰氧基脯氨酸衍生物，并将其用作环酮（环己酮和环戊酮）与几种取代的苯甲醛之间的直接不对称羟醛反应的催化剂。使用水进行反应，这是所检验的最佳反应介质。对这些催化剂的筛选表明，带有最多疏水性酰基链的化合物[4-苯基丁酸酯和4-（吡啶-1-基）丁酸酯]提供了更好的结果。后一种催化剂在室温下仅以2摩尔％的比例成功使用，无需添加添加剂，即可获得具有出色立体选择性的羟醛产物。这些结果表明脯氨酸部分在4-位上带有适当的简单疏水取代基的衍生化可以提供高活性和立体选择性的催化剂，而无需在分子中另外的手性主链。最后，提供了在水存在下观察到的立体选择性的解释。
• A Highly Efficient, Large-Scale, Asymmetric Direct Aldol Reaction Employing Simple Threonine Derivatives as Recoverable Organocatalysts in the Presence of Water
  作者：Chuanlong Wu、Xiangkai Fu、Shi Li

  DOI：10.1002/ejoc.201001396

  日期：2011.3

  A one-step O-acylation of threonine resulted in a simple and readily available threonine-surfactant organocatalyst that could efficiently catalyze the direct asymmetric aldol reactions of cyclic and acyclic ketones with a series of aromatic aldehydes in the presence of water at room temperature with good yields (up to 99 %), diastereoselectivities (up to 99:1), and enantiomeric excesses (>99 %). The

  苏氨酸的一步 O-酰化产生了一种简单易得的苏氨酸 - 表面活性剂有机催化剂，它可以在室温下在水的存在下有效地催化环状和非环状酮与一系列芳香醛的直接不对称醛醇反应。产率（高达 99%）、非对映选择性（高达 99:1）和对映体过量（>99%）。该催化剂可以很容易地回收和重复使用，六次循环后对映选择性不会降低。这种新型催化剂可以有效地用于大规模反应，同时对映选择性保持在同一水平，为工业应用提供了很大的可能性。
• Advances towards Highly Active and Stereoselective Simple and Cheap Proline-Based Organocatalysts
  作者：Francesco Giacalone、Michelangelo Gruttadauria、Paola Agrigento、Paolo Lo Meo、Renato Noto

  DOI：10.1002/ejoc.201000913

  日期：2010.10

  at loadings of 2–0.1 mol-% for the direct asymmetric aldol reaction in water by using variable amounts of water. Among them, a new catalyst, the L-proline carrying a trans-4-(2,2-diphenylacetoxy) group, and a catalyst previously synthesized by us, the L-proline carrying a trans-4-(4-phenylbutanoyloxy) group, were found to be excellent catalysts for the aldol reaction between cyclohexanone or cyclopentanone

  通过使用不同量的水，筛选出 10 种 4-酰氧基-L-脯氨酸作为催化剂，负载量为 2-0.1 mol-%，用于在水中的直接不对称羟醛反应。其中，新型催化剂L-脯氨酸带有反式4-(2,2-二苯基乙酰氧基)基团，以及我们之前合成的催化剂L-脯氨酸带有反式4-(4-苯基丁酰氧基)基团, 被发现是环己酮或环戊酮与取代苯甲醛之间羟醛反应的优良催化剂，当分别以 1 和 0.5 mol-% 在室温下使用时，没有添加剂。对于此类催化剂，获得了高转化率，这是烯胺有机催化获得的最高值之​​一。最后，这些催化剂可以通过廉价分子的直接 O-酰化合成，并成功用于放大反应。