(2S,1'R)-2-[(2,6-dichlorophenyl)hydroxymethyl]cyclohexan-1-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: (2S,1'R)-2-[(2,6-dichlorophenyl)hydroxymethyl]cyclohexan-1-one
• 英文别名: 2-((2,6-dichlorophenyl)(hydroxy)methyl)cyclohexanone；(S)-2-((R)-(2,6-dichlorophenyl)(hydroxy)methyl)cyclohexanone；(2S)-2-[(R)-(2,6-dichlorophenyl)-hydroxymethyl]cyclohexan-1-one
• 化学式: C₁₃H₁₄Cl₂O₂
• 分子量: 273.159
• InChiKey: FZYIXDFVZCYBSS-AMIZOPFISA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.6
• 重原子数：
  17
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.46
• 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：

  环己酮 、 2,6-二氯苯甲醛 在 trans-4-hydroxy-L-prolinamide derivative 作用下， 以 水 为溶剂， 反应 5.0h， 以95%的产率得到(2S,1'R)-2-[(2,6-dichlorophenyl)hydroxymethyl]cyclohexan-1-one
  参考文献：
  名称：

  水中的有机催化高度非对映和对映选择性直接羟醛反应

  摘要：

  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％。

  DOI：

  10.1016/j.tetlet.2008.03.131

文献信息

• Enamine-Metal Lewis Acid Bifunctional Catalysis: Application to Direct Asymmetric Aldol Reaction of Ketones
  作者：Zhenghu Xu、Philias Daka、Ilya Budik、Hong Wang、Fu-Quan Bai、Hong-Xing Zhang

  DOI：10.1002/ejoc.200900678

  日期：2009.9

  Unprecedented bifunctional enamine–metal Lewis acid catalysts have been developed. In this bifunctional catalytic system, a tridentate ligand tethered with a chiral secondary amine was designed to solve the acid–base self-quenching problem leading to catalyst inactivation. This new bifunctional enamine–metal Lewis acid catalyst was found to catalyze aldol reactions of ketones efficiently in high yields

  已经开发出前所未有的双功能烯胺-金属路易斯酸催化剂。在这种双功能催化系统中，设计了一种与手性仲胺相连的三齿配体，以解决导致催化剂失活的酸碱自淬灭问题。发现这种新型双功能烯胺-金属路易斯酸催化剂能够以高产率有效催化酮的羟醛反应，并具有良好到优异的非对映选择性和对映选择性。（© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009）
• SULFONAMIDE-BASED ORGANOCATALYSTS AND METHOD FOR THEIR USE
  申请人：Carter Rich Garrett

  公开号：US20100184986A1

  公开（公告）日：2010-07-22

  Organocatalysts, particularly proline sulfonamide organocatalysts, having a first general formula as follows are disclosed. Embodiments of a method for using these organocatalysts also are disclosed. The method comprises providing a disclosed organocatalyst, and performing a reaction, often an enantioselective or diastereoselective reaction, using the organocatalyst. Solely by way of example, disclosed catalysts can be used to perform aldol reactions, conjugate additions, Michael additions, Robinson annulations, Mannich reactions, α-aminooxylations, α-hydroxyaminations, α-aminations and alkylation reactions. Certain of such reactions are intramolecular cyclizations used to form cyclic compounds, such as 5- or 6-membered rings, having one or more chiral centers. Disclosed organocatalysts generally are much more soluble in typical solvents used for organic synthesis than are known compounds. Moreover, the reaction yield is generally quite good with disclosed compounds, as is their enantioselective and diastereoselective effectiveness.

  披露了具有如下一般公式之一的有机催化剂，尤其是脯氨酸磺酰胺有机催化剂。还披露了使用这些有机催化剂的方法的实施例。该方法包括提供一种披露的有机催化剂，并使用该有机催化剂进行反应，通常是立体选择性的反应或对映选择性反应。仅作为示例，披露的催化剂可用于进行aldol反应、共轭加成、Michael加成、Robinson环化反应、Mannich反应、α-氨基氧化、α-羟基胺化、α-胺化和烷基化反应。其中一些反应是分子内环化反应，用于形成具有一个或多个手性中心的环状化合物，例如5或6元环。披露的有机催化剂通常比已知的化合物更容易溶于用于有机合成的典型溶剂中。此外，使用披露化合物的反应收率通常相当好，它们的对映选择性和非对映选择性效果也很好。
• Primary amine-metal Lewis acid bifunctional catalysts: the application to asymmetric direct aldol reactions
  作者：Zhenghu Xu、Philias Daka、Hong Wang

  DOI：10.1039/b912728c

  日期：——

  The first example of metal Lewis acid-primary amine bifunctional cooperative catalyst derived from primary amino acids was developed, and it was found to catalyze aldol reactions of cyclic ketones highly efficiently with very good to excellent stereoselectivities.

  开发了衍生自伯氨基酸的金属路易斯酸-伯胺双官能协同催化剂的第一个实例，发现它可以非常有效地催化环状酮的醛醇缩合反应，具有非常好的至优异的立体选择性。
• <i>N</i>-(<i>p</i>-Dodecylphenylsulfonyl)-2-pyrrolidinecarboxamide: A Practical Proline Mimetic for Facilitating Enantioselective Aldol Reactions
  作者：Hua Yang、Rich G. Carter

  DOI：10.1021/ol801941j

  日期：2008.10.16

  A highly practical and readily available proline surrogate has been developed with improved solubility properties in common, nonpolar organic solvents. This sulfonamide-based catalyst has proven highly effective at facilitating enantioselective and diastereoselective aldol reactions with a range of substrates in nonpolar organic solvents in the presence of a single equivalent of water. Additionally

  一种高度实用且易于获得的脯氨酸替代品已被开发出来，其在常见非极性有机溶剂中的溶解度得到改善。事实证明，这种磺酰胺基催化剂在单当量水存在下，在非极性有机溶剂中能够非常有效地促进与一系列底物的对映选择性和非对映选择性羟醛反应。此外，在不存在任何有机溶剂的情况下，可以使用低至 2 mol% 的催化剂负载，并具有持续的高水平选择性。
• Highly Stereoselective and Scalable <i>anti</i>-Aldol Reactions Using <i>N</i>-(<i>p</i>-Dodecylphenylsulfonyl)-2-pyrrolidinecarboxamide: Scope and Origins of Stereoselectivities
  作者：Hua Yang、Subham Mahapatra、Paul Ha-Yeon Cheong、Rich G. Carter

  DOI：10.1021/jo1015008

  日期：2010.11.5

  A highly enantio- and diastereoselective anti-aldol process (up to >99% ee, >99:1 dr) catalyzed by a proline mimetic—N-(p-dodecylphenylsulfonyl)-2-pyrrolidinecarboxamide—has been developed. Catalyst loading as low as 2 mol % can be employed. Use of industry-friendly solvents for this transformation as well as neat reaction conditions have been demonstrated. The scope of this transformation on a range

  一种由脯氨酸模拟物N- (对十二烷基苯磺酰基)-2-吡咯烷甲酰胺催化的高度对映和非对映选择性反羟醛过程（高达 >99% ee，>99:1 dr）已被开发出来。可以使用低至2mol%的催化剂负载。已经证明可以使用工业友好型溶剂进行这种转化以及纯净的反应条件。探索了这种对一系列醛和酮的转化范围。密度泛函理论计算表明，增强的非对映选择性的起源是由于磺酰胺、亲电子试剂和催化剂烯胺之间存在非经典氢键，有利于 Houk−List 模型中主要的反 Re 醛醇TS 。