(4S,5R)-4,5-diphenyl-5-(trifluoromethyl)dihydrofuran-2(3H)-one | 1097643-66-7

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 二苯乙烯类
• 英文名称: (4S,5R)-4,5-diphenyl-5-(trifluoromethyl)dihydrofuran-2(3H)-one
• 英文别名: (4S,5R)-4,5-diphenyl-5-trifluoromethyl-dihydro-furan-2-one；(4S,5R)-4,5-Diphenyl-5-(trifluoromethyl)tetrahydrofuran-2-one；(4S,5R)-4,5-diphenyl-5-(trifluoromethyl)oxolan-2-one
• CAS: 1097643-66-7
• 化学式: C₁₇H₁₃F₃O₂
• 分子量: 306.284
• InChiKey: SEMYUNFBRXNNTK-HOCLYGCPSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4
• 重原子数：
  22
• 可旋转键数：
  2
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.24
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  (4S,5R)-4,5-diphenyl-5-(trifluoromethyl)dihydrofuran-2(3H)-one 、 R(+)-alpha-甲基苄胺 以 甲醇 为溶剂， 反应 9.0h， 生成 (3S,4R,1'R)-5,5,5-trifluoro-4-hydroxy-3,4-diphenyl-pentanoic acid (1-phenyl-ethyl)-amide
  参考文献：
  名称：

  具有平面手性的环烷型咪唑鎓盐是一类新的N杂环卡宾前体。

  摘要：

  由对映体纯的2-氨基醇合成了具有平面手性的环烷型咪唑鎓盐，其中N（1）和N（3）位置通过桥连接。咪唑鎓盐及其衍生物N-杂环卡宾（NHCs）的结构轮廓通过数种分析方法进行了研究。已发现衍生自这些咪唑鎓盐的手性NHC借助烯类的“共轭”蛋白酚催化酮类的α，β-不饱和醛与酮的不对称交叉环化，从而得到具有良好或优异性能的目标γ-内酯对映选择性（高达94％ee）。基于NHC及其中间体的预期结构，以及产品的绝对构型，提出了一种可行的立体控制机制。

  DOI：

  10.1002/chem.200800942
• 作为产物：
  描述：

  2,2,2-三氟苯乙酮 、 肉桂醛 在 C₁₇H₁₇N₂⁽¹⁺⁾*ClO₄^(1-) 、 1,8-二氮杂双环[5.4.0]十一碳-7-烯 作用下， 以 甲苯 为溶剂， 反应 24.0h， 以10%的产率得到
  参考文献：
  名称：

  Asymmetric induction afforded by chiral azolylidene N-heterocyclic carbenes (NHC) catalysts

  摘要：

  Screening studies of new chiral imidazolium and triazolium based NHC salts I-VIII as ligands in asymmetric organometallic catalysis and as organocatalysts showed that these catalysts efficiently promoted the reactions. Moderate enantioselectivities (55-57% ee) were obtained in the asymmetric Cu-NHC catalysed conjugate additions of diethylzinc to cyclohexenone, in accordance with most previous studies. The chiral induction afforded in the gold(I)-NHC catalysed cyclopropanation reactions was low (< 28% ee). However, these results represent the first reported chiral gold(I)-NHC catalysed olefin cyclopropanation. The NHC-organocatalysed asymmetric cross-annulation of cinnamaldehyde and trifluoroacetophenone gave lower enantioselectivity (< 50% ee) but higher yields of the gamma-lactone product relative to previous reports. The enantioselectivities obtained varied considerably, even within a group of structurally closely related NHCs. This study demonstrates the challenge of designing NHCs with a general ability to induce asymmetry in a broader range of reactions. (C) 2012 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetasy.2012.09.004

文献信息

• β-Carbon activation of saturated carboxylic esters through N-heterocyclic carbene organocatalysis
  作者：Zhenqian Fu、Jianfeng Xu、Tingshun Zhu、Wendy Wen Yi Leong、Yonggui Robin Chi

  DOI：10.1038/nchem.1710

  日期：2013.10

  The activation of the α-carbons of carboxylic esters and related carbonyl compounds to generate enolate equivalents as nucleophiles is one of the most powerful strategies in organic synthesis. We reasoned that the horizons of chemical synthesis could be greatly expanded if the typically inert β-carbons of saturated esters could be used as nucleophiles. However, despite the rather significant fundamental

  活化羧酸酯和相关羰基化合物的 α-碳以生成烯醇等价物作为亲核试剂是有机合成中最有效的策略之一。我们推断，如果饱和酯的典型惰性 β-碳可以用作亲核试剂，则化学合成的范围可以大大扩展。然而，尽管具有相当重要的基本和实用价值，但直接使用饱和羰基化合物的 β-碳作为亲核试剂仍然难以捉摸。在这里，我们报告了使用N催化活化作为亲核试剂的简单饱和酯 β-碳（β-碳活化）-杂环卡宾有机催化剂。催化产生的亲核β-碳与亲电子试剂如烯酮和亚胺发生对映选择性反应。鉴于已证明酯 α-碳具有丰富的化学性质，我们预计这种饱和酯 β-碳的催化活化模式将为新的有用反应和合成策略开辟一个有价值的新领域。
• Chiral bicyclic imidazolium salts as a new class of N-heterocyclic carbene precursors
  作者：Yuki Matsuoka、Yasuhiro Ishida、Kazuhiko Saigo

  DOI：10.1016/j.tetlet.2008.02.175

  日期：2008.4

  bridged chiral bicyclic imidazole with a morpholine framework was synthesized from an enantiopure 2-amino alcohol. The resultant imidazole reacted with various electrophiles, including primary and secondary alkyl halides, benzyne, and an electron-deficient aryl halide, to give the corresponding imidazolium salts. Some of the imidazolium salts were found to have potential as the precursor of a chiral N-heterocyclic

  由对映体纯的2-氨基醇合成了具有吗啉骨架的AN（1）–C（5）桥接手性双环咪唑。所得咪唑与各种亲电试剂反应，包括伯和仲烷基卤化物，苯并炔和缺电子的芳基卤化物，得到相应的咪唑鎓盐。发现一些咪唑鎓盐具有作为手性N-杂环卡宾催化剂的前体的潜能。通过将烯醇和酮通过均烯酸酯和活化的羧酸酯的中间体直接环化，以对映体富集的形式（高达ee的66％）获得目标内酯。
• [EN] ACTIVATION OF CARBONYL &bgr;-CARBONS FOR CHEMICAL TRANSFORMATIONS<br/>[FR] ACTIVATION DE &Bgr;-CARBONES DE CARBONYLE POUR DES TRANSFORMATIONS CHIMIQUES
  申请人：UNIV NANYANG TECH

  公开号：WO2014142755A1

  公开（公告）日：2014-09-18

  The present invention relates to a method for synthesizing a compound of Formula (I) as defined herein, comprising: (i) activating a compound of Formula (II) as defined herein, by reacting said compound of Formula (II) with a compound of Formula (III) as defined herein, in the presence of a base, to obtain a compound of Formula (IV) as defined herein; and (ii) reacting the compound of Formula (IV) with an electrophile to obtain the compound of Formula (I). The present invention further relates to the organocatalysts used in the described methods and their respective uses.

  本发明涉及一种合成式(I)化合物的方法，包括：(i) 通过在碱的存在下，将式(II)化合物与式(III)化合物反应，激活式(II)化合物，以得到式(IV)化合物；以及(ii) 通过将式(IV)化合物与亲电试剂反应，得到式(I)化合物。本发明还涉及所述方法中使用的有机催化剂及其相应的用途。
• Enantio- and Diastereoselective Cross-annulation of Enal and Ketone with New Chiral Bicyclic <i>N</i>-Heterocyclic Carbene Catalysts
  作者：Momo Hasegawa、Kazuhiro Yoshida、Akira Yanagisawa

  DOI：10.1246/cl.151116

  日期：2016.3.5

  The enantio- and diastereoselective cross-annulation of cinnamaldehyde (6) and 2,2,2-trifluoroacetophenone (7) was examined to evaluate the performance of newly developed chiral bicyclic imidazolium salts 3 and 4 as catalyst precursors. The reaction proceeded to give desired γ-lactone 8 with high diastereoselectivities (up to 10/1) and moderate enantioselectivities (up to 71% ee) when the sterically demanding catalyst precursors were used.

  对肉桂醛（6）和2,2,2-三氟苯乙酮（7）的对应和立体选择性交叉消旋进行了研究，以评估新开发的作为催化剂前体的手性双环咪唑鎓盐3和4的性能。当使用空间要求苛刻的催化剂前体时，反应产生了具有高立体选择性（高达10/1）和中等对映选择性（高达71% ee）的所需γ-内酯8。
• Activation of carbonyl beta-carbons for chemical transformations
  申请人：Nanyang Technological University

  公开号：US11306097B2

  公开（公告）日：2022-04-19

  The present invention relates to a method for synthesizing a compound of Formula (I) as defined herein, comprising: (i) activating a compound of Formula (II) as defined herein, by reacting said compound of Formula (II) with a compound of Formula (III) as defined herein, in the presence of a base, to obtain a compound of Formula (IV) as defined herein; and (ii) reacting the compound of Formula (IV) with an electrophile to obtain the compound of Formula (I). The present invention further relates to the organocatalysts used in the described methods and their respective uses.

  本发明涉及一种合成式（I）化合物的方法 的方法，包括： (i) 活化式（II）化合物 将所述式 (II) 化合物与式 (III) 化合物反应，得到如本文所定义的化合物 如本文所定义，在碱存在下，得到式（IV）化合物 如本文所定义；以及(ii)使式(IV)化合物与亲电子体反应，得到式(I)化合物。本发明进一步涉及所述方法中使用的有机催化剂及其各自的用途。