(R)-1-(4-chlorophenyl)-4,4,4-trifluoro-3-hydroxybutan-1-one

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (R)-1-(4-chlorophenyl)-4,4,4-trifluoro-3-hydroxybutan-1-one
• 英文别名: (R)-4,4,4-trifluoro-3-hydroxy-1-(4-chlorophenyl)-1-butanone；(3R)-1-(4-chlorophenyl)-4,4,4-trifluoro-3-hydroxybutan-1-one
• 化学式: C₁₀H₈ClF₃O₂
• 分子量: 252.621
• InChiKey: AJAUFTJAMJLQJM-SECBINFHSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.7
• 重原子数：
  16
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.3
• 拓扑面积：
  37.3
• 氢给体数：
  1
• 氢受体数：
  5

反应信息

• 作为产物：
  描述：

  3-(4-chlorophenyl)-3-oxopropanoic acid 在 copper(l) iodide 、 (R,R)-2,2'-异亚丙基双(4-苯基-2-恶唑啉) 作用下， 以 甲苯 为溶剂， 反应 148.0h， 以86%的产率得到
  参考文献：
  名称：

  铜催化的β-酮酸与三氟重氮乙烷的一锅脱氮-脱氢-脱羧偶联：容易获得三氟甲基化的羟醛产品

  摘要：

  已经开发了一种新型的铜催化的β-酮酸与原位生成的三氟重氮乙烷的单锅交叉偶联。该反应提供了一种直接和有效的方法，其中，一种C  C键和一种C 形成在伴随脱氮-脱氢-脱羧卡宾中心O键，得到三氟甲基化的醛醇产品。在一些初步实验中，还获得了良好的对映选择性。

  DOI：

  10.1002/chem.201403073

文献信息

• <i>C</i>₂-Symmetric Chiral Bisoxazolines as Hydrogen-Bond-Acceptor Catalysts in Enantioselective Aldol Reaction of β-Carbonyl Acids with Trifluoroacetaldehyde Hemiacetals
  作者：Zhen-Yan Yang、Jun-Liang Zeng、Nan Ren、Wei Meng、Jing Nie、Jun-An Ma

  DOI：10.1021/acs.orglett.6b03256

  日期：2016.12.16

  C2-symmetric chiral bisoxazoline is demonstrated to use hydrogen bonding to catalyze an important family of aldol reactions of trifluoroacetaldehyde hemiacetals with various β-carbonyl acids. This reaction is highly enantioselective, delivering chiral nonracemic trifluoromethylated alcohols with excellent optical purity and good isolated yields. This concept of relaying chiral information via a chiral hydrogen-bond

  一个简单的C 2对称手性双恶唑啉被证明使用氢键催化三氟乙醛半缩醛与各种β-羰基酸的重要的醛醇缩合反应家族。该反应是高度对映体选择性的，以优异的光学纯度和良好的分离产率提供手性非外消旋三氟甲基化醇。通过手性氢键受体传递手性信息的概念应适用于大量的有机催化过程。
• Chiral bifunctional thiourea-catalyzed enantioselective aldol reaction of trifluoroacetaldehyde hemiacetal with aromatic ketones
  作者：Jing Nie、Xiao-Juan Li、Dong-Hua Zheng、Fa-Guang Zhang、Shumin Cui、Jun-An Ma

  DOI：10.1016/j.jfluchem.2011.04.019

  日期：2011.7

  the direct aldol condensation of trifluoroacetaldehyde methyl hemiacetal with aromatic ketones proceeds to produce (R)-β-hydroxy β-trifluoroalkyl ketones in low to moderate yields with good enantioselectivities.

  在糖衍生的双官能胺-硫脲催化剂的存在下，三氟乙醛甲基半缩醛与芳族酮的直接羟醛缩合进行以低到中等的产率产生具有良好对映选择性的（R）-β-羟基β-三氟烷基酮。
• Process for producing 4,4,4,- trifluoro-3-hydroxybutyric acid
  申请人：CENTRAL GLASS COMPANY, LIMITED

  公开号：US20030088095A1

  公开（公告）日：2003-05-08

  A first process for producing an optically active perfluoroalkylcarbinol derivative includes (a) reacting an optically active imine with a compound that is a hemiacetal of a perfluoroalkylaldehyde or a hydrate of a perfluoroalkylaldehyde to obtain a condensate; and (b) hydrolyzing the condensate under an acid condition. A second process for increasing optical purity of an optically active 4,4,4-trifluoro 3-hydroxy-1-aryl-1-butanone derivative includes (a) precipitating a racemic crystal of the derivative, from the derivative; and (b) removing the racemic crystal from the derivative. A third process for increasing optical purity of the butanone derivative includes recrystallizing the derivative. Novel compounds are optically active and inactive 4,4,4-trifluoro-3-hydroxybutanoic aryl ester derivatives. A fourth process for producing an optically active or optically inactive 4,4,4-trifluoro-3-hydroxybutyric acid aryl ester derivative includes oxidizing an optically active or optically inactive 4,4,4-trifluoro-3-hydroxy-1-aryl-1-butanone derivative. A fifth process for increasing optical purity of the optically active aryl ester derivative includes recrystallizing the derivative. A sixth process for producing an optically active 4,4,4-trifluoro-1,3-butanediol includes reducing the optically active aryl ester derivative by a hydride. A seventh process for producing an optically active or inactive 4,4,4-trifluoro-3-hydroxybutyric acid alkyl ester derivative includes reacting under an acid condition the optically active or optically inactive aryl ester derivative with a lower alcohol. It is possible to suitably combine at least two of the first to seventh processes.

  生产光学活性全氟烷基羟基甲基醇衍生物的第一种方法包括（a）将光学活性亚胺与半乙醇的全氟烷基醛或全氟烷基醛的水合物反应，以获得缩合物; （b）在酸性条件下水解缩合物。增加光学纯度的光学活性4,4,4-三氟-3-羟基-1-芳基-1-丁酮衍生物的第二种方法包括（a）从该衍生物中沉淀出外消旋晶体; （b）将外消旋晶体从衍生物中去除。增加丁酮衍生物光学纯度的第三种方法包括重结晶该衍生物。新化合物是光学活性和非活性的4,4,4-三氟-3-羟基丁酸芳基酯衍生物。生产光学活性或非活性的4,4,4-三氟-3-羟基丁酸芳基酯衍生物的第四种方法包括将光学活性或非活性的4,4,4-三氟-3-羟基-1-芳基-1-丁酮衍生物氧化。增加光学活性芳基酯衍生物光学纯度的第五种方法包括重结晶该衍生物。生产光学活性4,4,4-三氟-1,3-丁二醇的第六种方法包括通过氢化还原光学活性芳基酯衍生物。生产光学活性或非活性的4,4,4-三氟-3-羟基丁酸烷基酯衍生物的第七种方法包括在酸性条件下将光学活性或非活性的芳基酯衍生物与低级醇反应。可以适当地组合第一至第七种方法中的至少两种方法。
• Organocatalytic Asymmetric Direct Aldol Reactions of Trifluoroacetaldehyde Ethyl Hemiacetal with Aromatic Methyl Ketones
  作者：Kazumasa Funabiki、Yuya Itoh、Yasuhiro Kubota、Masaki Matsui

  DOI：10.1021/jo200020z

  日期：2011.5.6

  The organocatalytic asymmetric direct aldol reaction of trifluoroacetaldehyde ethyl hemiacetal with aromatic methyl ketones in the presence of a catalytic amount of (S)-5-(pyrrolidin-2-yl)-1H-tetrazole in dichloroethane at 40 °C proceeds smoothly to produce (R)-4,4,4-trifluoro-1-aryl-3-hydroxy-1-butanones in high yields with up to 90% ee.

  三氟乙醛乙基半缩醛与芳族甲基酮在催化量的（S）-5-（吡咯烷-2-基）-1 H-四唑在二氯乙烷中的存在下于40°C进行有机催化的不对称直接醛醇缩合反应顺利进行，得到了（R）-4,4,4-三氟-1-芳基-3-羟基-1-丁酮，高收率，ee高达90％。
• Practical asymmetric synthesis of β-hydroxy-β-trifluoromethylated ketones via the first example of the in situ generation of trifluoro-acetaldehyde and its successive asymmetric carbon–carbon bond formation reaction with chiral imines
  作者：Kazumasa Funabiki、Wataru Hashimoto、Masaki Matsui

  DOI：10.1039/b408226e

  日期：——

  Not only trifluoroactaldehyde ethyl hemiacetal or hydrate but also other polyfluoroalkylaldehydes acetals or hydrates react with an equimolar amount of various chiral imines, followed by hydrolysis to produce the corresponding (S)-beta-hydroxy-beta-polyfluoroalkyl ketones in good yields with good enantioselectivities; furthermore, the ee of the products can be improved by simple recrystallization.

  不仅三氟乙醛乙基半缩醛或水合物，而且其他多氟烷基醛缩醛或水合物也与等摩尔量的各种手性亚胺反应，然后水解生成相应的（S）-β-羟基-β-多氟烷基酮，并具有良好的收率和良好的对映选择性。此外，可以通过简单的重结晶来改善产物的ee。