(R)-ethyl 2-hydroxy-4-phenyl-2-(trifluoromethyl)pent-4-enoate | 957503-42-3

• 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: (R)-ethyl 2-hydroxy-4-phenyl-2-(trifluoromethyl)pent-4-enoate
• 英文别名: ethyl (2R)-2-hydroxy-4-phenyl-2-(trifluoromethyl)pent-4-enoate
• CAS: 957503-42-3
• 化学式: C₁₄H₁₅F₃O₃
• 分子量: 288.267
• InChiKey: ZCFSHRWRZZIQOB-CYBMUJFWSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.8
• 重原子数：
  20
• 可旋转键数：
  6
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.36
• 拓扑面积：
  46.5
• 氢给体数：
  1
• 氢受体数：
  6

反应信息

• 作为产物：
  描述：

  苯乙酮 在 silver hexafluoroantimonate 、 PdCl₂[(S)-SunPhos] 、 potassium tert-butylate 作用下， 以 四氢呋喃 、 乙二醇二甲醚 、 1,2-二氯乙烷 为溶剂， 反应 19.5h， 生成 (S)-ethyl 2-hydroxy-4-phenyl-2-(trifluoromethyl)pent-4-enoate 、 (R)-ethyl 2-hydroxy-4-phenyl-2-(trifluoromethyl)pent-4-enoate
  参考文献：
  名称：

  Pd（II）-SunPhos配合物催化三氟丙酮酸的不对称羰基-烯反应

  摘要：

  开发了一种有效的手性Pd（II）/（S）-SunPhos配合物催化的三氟丙酮酸不对称羰基-烯反应。在温和条件下以高收率和优异的ee获得了一系列包含CF 3基团的光学活性均烯丙基醇。特别地，异丁烯和三氟丙酮酸酯的反应得到所需产物（90％收率，98％ee），催化剂在二氯乙烷/甲苯中的负载量低至0.01mol％。

  DOI：

  10.1016/j.tet.2017.10.044

文献信息

• Chiral Bis(imidazolinyl)phenyl NCN Pincer Rhodium(III) Catalysts for Enantioselective Allylation of Aldehydes and Carbonyl–Ene Reaction of Trifluoropyruvates
  作者：Tao Wang、Xin-Qi Hao、Juan-Juan Huang、Jun-Long Niu、Jun-Fang Gong、Mao-Ping Song

  DOI：10.1021/jo4014194

  日期：2013.9.6

  Chiral NCN pincer rhodium(III) complexes with bis(imidazolinyl)phenyl ligands were found to be effective catalysts for the allylation of a variety of electronically and structurally diverse aldehydes with allyltributyltin, giving the corresponding optically active homoallylic alcohols in high yields with enantioselectivities of up to 97% ee. These complexes were also applied in the carbonyl–ene reaction

  发现具有双（咪唑啉基）苯基配体的手性NCN钳形铑（III）配合物是有效的催化剂，用于将各种电子和结构不同的醛与烯丙基三丁基锡进行烯丙基化，从而以高收率得到相应的光学活性均烯醇，且对映选择性高达到97％ee。这些配合物还用于三氟丙酮酸乙酯或三氟丙酮酸甲酯与各种2-芳基丙烯的羰基-烯反应中。借助三氟甲磺酸银，钳型铑（III）催化剂可以催化反应，以高收率和高立体选择性（最高95％ee）提供相应的手性α-羟基-α-三氟甲基酯。
• Tandem ionic liquid antimicrobial toxicity and asymmetric catalysis study: carbonyl-ene reactions with trifluoropyruvate
  作者：Rohitkumar G. Gore、Thi-Kim-Thu Truong、Milan Pour、Lauren Myles、Stephen J. Connon、Nicholas Gathergood

  DOI：10.1039/c3gc40875b

  日期：——

  The asymmetric carbonyl-ene reaction of trifluoropyruvate with five alkenes catalysed by [Pd(R)-BINAP}](SbF6)2 were carried out in good yields and enantioselectivities (up to 96% yield and 96% ee) in low antimicrobial toxicity C2-substituted imidazolium ionic liquids (ILs). Toxicity data was included in the selection criteria for reaction optimisation after a preliminary IL screen. The Pd(II) catalyst immobilised in an IL was recycled and reused up to 7 times without decrease of either yield or ee. One IL prepared, which was determined to be of high antimicrobial toxicity was assigned a low priority for future applications.

  在低抗菌毒性的C2取代咪唑鎓离子液体（ILs）中，三氟丙酮酸与五种烯烃的非对称羰基-烯反应在[Pd(R)-BINAP}](SbF6)2催化下，实现了良好的产率和立体选择性（最高达96%产率和96% ee）。在初步的IL筛选后，毒性数据被纳入反应优化的选择标准。固定在IL中的Pd(II)催化剂可回收并重复使用多达7次，且产率和ee均无下降。一种制备的IL被确定具有高抗菌毒性，因此被赋予低优先级用于未来的应用。
• Asymmetric Latent Carbocation Catalysis with Chiral Trityl Phosphate
  作者：Jian Lv、Qichao Zhang、Xingren Zhong、Sanzhong Luo

  DOI：10.1021/jacs.5b11085

  日期：2015.12.16

  Stable carbocations such as tritylium ions have been widely explored as organic Lewis acid catalysts and reagents in organic synthesis. However, achieving asymmetric carbocation catalysis remains elusive ever since they were first identified over one century ago. The challenges mainly come from their limited compatibility, scarcity of chiral carbocations, as well as the extremely low barrier to racemization

  稳定的碳正离子如三苯甲基离子已被广泛用作有机合成中的有机路易斯酸催化剂和试剂。然而，自从一个多世纪前首次发现它们以来，实现不对称碳正离子催化仍然难以实现。挑战主要来自它们有限的相容性、手性碳正离子的稀缺性以及极低的手性碳正离子外消旋化障碍。我们在这里报告了不对称碳正离子催化的潜在概念。在该策略中，手性磷酸三苯甲基酯用作碳阳离子前体，在温和的外部刺激（例如酸、氢键、极性底物）下容易发生离子解离，形成具有催化活性的手性离子对，用于底物活化和手性诱导。
• Asymmetric Calcium Catalysis: Highly Enantioselective Carbonyl-Ene and Friedel-Crafts Reactions for the Synthesis of Quaternary α-Hydroxy Esters Bearing a Trifluoromethyl Group
  作者：Magnus Rueping、Teerawut Bootwicha、Supakeat Kambutong、Erli Sugiono

  DOI：10.1002/asia.201200063

  日期：2012.6

  Enantioselective calcium‐catalyzed addition reactions of styrene and indole derivatives with trifluoropyruvates have been developed. The alkaline‐earth metal‐catalyzed reactions proceed smoothly to afford the corresponding products in high yields and with good to excellent enantioselectivities under mild reaction conditions.

  已经开发了苯乙烯和吲哚衍生物与三氟丙酮酸盐的对映选择性钙催化加成反应。在温和的反应条件下，碱土金属催化的反应可顺利进行，从而以高收率提供良好的对映选择性，得到相应的产物。
• Asymmetric carbonyl-ene and Friedel–Crafts reactions catalysed by Lewis acid platinum group metal complexes of the enantiopure atropisomeric biaryl-like diphosphine (S)-Me2-CATPHOS: a comparison with BINAP
  作者：Simon Doherty、Julian G. Knight、Hamid Mehdi-Zodeh

  DOI：10.1016/j.tetasy.2012.01.022

  日期：2012.2

  Lewis acid platinum and palladium complexes of (S)-Me-2-CATPHOS catalyse the carbonyl-ene reaction between allylbenzene derivatives and ethyl trifluoropyruvate to give the expected alpha-hydroxy esters with ee's up to 97%, while the corresponding reaction involving 2-allylfuran and thiophene was exclusively selective for Friedel-Crafts-type reactivity and gave the corresponding 2-hydroxy-trifluoromethyl ethyl esters in good yield and moderate to good enantioselectivity. (C) 2012 Elsevier Ltd. All rights reserved.