(2S)-2-[(R)-(4-fluorophenyl)(hydroxy)methyl]cyclopentanone | 1394033-17-0

• 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: (2S)-2-[(R)-(4-fluorophenyl)(hydroxy)methyl]cyclopentanone
• 英文别名: 2-[hydroxy-(4-fluoro-phenyl)methyl]-cyclopentanone；2-[(4-fluorophenyl)(hydroxy)methyl]cyclopentanone；(S)-2-((R)-(4-fluorophenyl)(hydroxy)methyl)cyclopentan-1-one；(S)-2-((R)-hydroxy(4-fulorophenyl)methyl)cyclopentanone；(2S)-2-[(R)-(4-fluorophenyl)-hydroxymethyl]cyclopentan-1-one
• CAS: 1394033-17-0
• 化学式: C₁₂H₁₃FO₂
• 分子量: 208.232
• InChiKey: RRMNLTZFRCOUDP-PWSUYJOCSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.9
• 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：
  3

反应信息

• 作为产物：
  描述：

  对氟苯甲醛 、 环戊酮 在 benzyl 3,4,6-tri-O-benzyl-2-deoxy-2-(L-prolylamino)-α-D-glucopyranoside 作用下， 反应 15.0h， 以71%的产率得到
  参考文献：
  名称：

  单糖衍生物的合成与表征及糖基脯氨酰胺在不对称合成中的应用

  摘要：

  首次合成、分离和使用N-乙酰氨基葡萄糖衍生物甲基2-乙酰氨基-3,4,6-三-O-苄基-2-脱氧-β-D-吡喃葡萄糖苷(9b)的β-异头体用于合成糖基伯胺4b。糖基伯胺 5a、一对单糖衍生物 6a 和 6b 以及所有这些化合物的前体也被合成、分离并通过标准光谱方法进行了充分研究，包括 1H-1H COZY 和 HSQC 等 2D NMR 光谱实验. 然后将糖基伯胺 4a、5a、6a 和 6b 以高产率转化为相应的脯氨酰胺有机催化剂（即 1a、2a、3a 和 3b）。这些糖基脯氨酰胺有机催化剂的催化活性在各种溶剂和不同温度下的不对称羟醛反应中得到证明。

  DOI：

  10.1002/ejoc.201200522

文献信息

• Synthesis and Characterization of Monosaccharide Derivatives and Application of Sugar-Based Prolinamides in Asymmetric Synthesis
  作者：Jyoti Agarwal、Rama Krishna Peddinti

  DOI：10.1002/ejoc.201200522

  日期：2012.11

  were converted into the corresponding prolinamide organocatalysts (i.e., 1a, 2a, 3a, and 3b) in high yields. The catalytic activity of these sugar-based prolinamide organocatalysts was demonstrated in asymmetric aldol reactions in various solvents and at different temperatures. The oraganocatalyst 3a was shown to be an efficient and powerful organocatalyst for the enantioselective aldol reaction of various

  首次合成、分离和使用N-乙酰氨基葡萄糖衍生物甲基2-乙酰氨基-3,4,6-三-O-苄基-2-脱氧-β-D-吡喃葡萄糖苷(9b)的β-异头体用于合成糖基伯胺4b。糖基伯胺 5a、一对单糖衍生物 6a 和 6b 以及所有这些化合物的前体也被合成、分离并通过标准光谱方法进行了充分研究，包括 1H-1H COZY 和 HSQC 等 2D NMR 光谱实验. 然后将糖基伯胺 4a、5a、6a 和 6b 以高产率转化为相应的脯氨酰胺有机催化剂（即 1a、2a、3a 和 3b）。这些糖基脯氨酰胺有机催化剂的催化活性在各种溶剂和不同温度下的不对称羟醛反应中得到证明。
• Synergistic effects within a C2-symmetric organocatalyst: the potential formation of a chiral catalytic pocket
  作者：Joshua P. Delaney、Hannah L. Brozinski、Luke C. Henderson

  DOI：10.1039/c3ob27250h

  日期：——

  This study describes the synthesis of five novel C2-symmetric organocatalysts that facilitate the on-water asymmetric aldol reaction at low catalyst loading (1 mol%) without the use of additives. Each catalyst is composed of two diprolinamide units joined by a symmetric alkyl bridging group allowing for systematic modulation of catalytic site proximity. Typically, catalysts in this manuscript which bear the catalytic units in close proximity gave the best reaction outcomes in terms of conversion (up to >99%), diastereomeric ratio (4/96, syn/anti) and enantiomeric excess (up to 97%). This effect has been attributed to the assembly of a chiral pocket, facilitated by hydrogen bonding at the oil-in-water interface.

  本研究介绍了五种新型 C2 对称有机催化剂的合成，这些催化剂可在不使用添加剂的情况下，以较低的催化剂负载量（1 摩尔%）促进水上不对称醛醇反应。每种催化剂都由两个二烯丙基酰胺单元组成，并由一个对称的烷基桥基连接，从而可以系统地调节催化位点的邻近性。通常情况下，本手稿中催化位点距离较近的催化剂在转化率（高达 >99%）、非对映异构体比率（4/96，同/反）和对映异构体过量（高达 97%）方面的反应效果最好。这种效果归因于在水包油界面的氢键作用下形成的手性口袋。
• Copolymer-supported heterogeneous organocatalyst for asymmetric aldol addition in aqueous medium
  作者：Jinqing Zhou、Jinwei Wan、Xuebing Ma、Wei Wang

  DOI：10.1039/c2ob25106j

  日期：——

  conditions. Compared with cyclohexanone, cyclopentanone and acetone showed the less desired enantioselectivities in the same aldol reactions. At the end of the aldol reaction, the copolymer-supported organocatalyst 1a was readily recovered in 95–98% yield from reaction mixture by simple filtration using an organic membrane. Even in the fifth run, there was no significant loss in catalytic activity and stereocontrol

  在当前的研究中，提出了一种方便和简单的方法，以AIBN为自由基引发剂，将9-氨基-9-脱氧-表位-辛可宁有机催化剂与丙烯腈共聚，以21-81％的产率合成新型负载型多相有机催化剂。。共聚物1a–d的化学组成（x / y）和重均分子量分别通过1 H NMR和GPC分析确定。它们的多孔和层状结构以及表面形貌通过氮吸附-解吸，XRD和TEM表征。在水中对硝基苯甲醛与对硝基苯甲醛的不对称醛醇加成反应中，所有负载的有机催化剂1a–d可提供出色的分离产率（90.2–94.7％）和立体选择性（96.8–97.8％ee抗，抗/ syn = 91/9）。在优化的条件下，在水中作为唯一的溶剂可获得最高的催化性能（96％的收率，抗/ syn = 90/10和99％ee抗）。与环己酮相比，环戊酮和丙酮在相同的羟醛反应中显示出较低的对映选择性。在醛醇缩合反应结束时，共聚物负载的有机催化剂1a通过使用有机膜的简单过滤，
• Both Amide-Bearing α- and β-Amino Acids from Natural Aspartic Acid Are Efficient Organocatalysts for Enantioselective Aldol Reactions
  作者：Gen-Fa Wen、Rui Zhang、Chao-Shan Da、Chu-Yu Zhang

  DOI：10.1055/a-1953-1656

  日期：2023.2

  of structurally similar α- and β-amino acids in an asymmetric aldol transformation. Interestingly, aspartic acid is not only an α-amino acid, but also a β-amino acid. Thus, by modifying one of the two acidic groups of aspartic acid, two sets of α- and β-amino acids, 14 amino acids in total, were prepared and used as organocatalysts. The two types of amino acid, interestingly, achieved similar high catalytic

  这项工作旨在比较和探索结构相似的α-和β-氨基酸在不对称醛醇转化中的不同催化效率。有趣的是，天冬氨酸不仅是一种α-氨基酸，也是一种β-氨基酸。因此，通过修饰天冬氨酸的两个酸性基团之一，制备了两组α-和β-氨基酸，总共14个氨基酸，并用作有机催化剂。有趣的是，这两种氨基酸在不同的最佳条件下在不对称醛醇转化中实现了相似的高催化效率。在某些情况下，理想的 β-氨基酸甚至比理想的 α-氨基酸实现了显着更高的对映选择性，尽管 α-氨基酸在这种不对称转化中被广泛证明是高效的有机催化剂。
• Direct asymmetric aldol reactions catalysed by trans-4-hydroxy-(S)-prolinamide in solvent-free conditions
  作者：Geeta Devi Yadav、Surendra Singh

  DOI：10.1016/j.tetasy.2015.09.003

  日期：2015.11

  Direct asymmetric aldol reactions between 4-nitrobenzaldehyde and cyclohexanone were catalysed by trans-4-hydroxy-(S)-prolinamide (10 mol %) in the presence of CH3COOH (10 mol %) as the co-catalyst under solvent-free conditions at 15 degrees C. (2S,4R)-4-Hydroxy-N-((S)-1-phenylethyl)pyrrolidine-2-carboxamide 2 efficiently, catalysed the asymmetric aldol reaction to afford the product in >99% yield and with 95% ee with an antilsyn ratio of 88:12 after 18 h. The additional trans-hydroxyl group on (S)-prolinamide and (S)-1-phenylethylamine both influenced the ee of the predominant anti aldol product. Different benzaldehyde derivatives with cyclohexanone gave the corresponding aldol products in 38-89% yields and with 56-94% ee with antilsyn (100:0-71:29). Catalyst 2 can be used up to 5 continuous cycles for asymmetric aldol reactions between 4-nitrobenzaldehyde and cyclohexanone with overall 91% yield and 86% yield of anti-product with anti/syn (98:2). (C) 2015 Elsevier Ltd. All rights reserved.