(1R,2R)-1,2-bis(4-(trifluoromethyl)phenyl)ethane-1,2-diol | 213776-03-5

• 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: (1R,2R)-1,2-bis(4-(trifluoromethyl)phenyl)ethane-1,2-diol
• 英文别名: (R,R)-(+)-1,2-bis(4-trifluoromethylphenyl)ethane-1,2-diol；(R,R)-1,2-bis(4-trifluoromethylphenyl)ethane-1,2-diol；1,2-bis(4-(trifluoromethyl)phenyl)ethane-1,2-diol；1,2-Ethanediol, 1,2-bis[4-(trifluoromethyl)phenyl]-, (1R,2R)-；(1R,2R)-1,2-bis[4-(trifluoromethyl)phenyl]ethane-1,2-diol
• CAS: 213776-03-5
• 化学式: C₁₆H₁₂F₆O₂
• 分子量: 350.26
• InChiKey: DIPRJPNCVRBSTA-ZIAGYGMSSA-N

物化性质

• 沸点：
  392.8±37.0 °C(Predicted)
• 密度：
  1.421±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.3
• 重原子数：
  24
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.25
• 拓扑面积：
  40.5
• 氢给体数：
  2
• 氢受体数：
  8

反应信息

• 作为反应物：
  描述：

  三光气 、 (1R,2R)-1,2-bis(4-(trifluoromethyl)phenyl)ethane-1,2-diol 在 吡啶 作用下， 以 二氯甲烷 为溶剂， 以70%的产率得到(R,R)-(+)-4,5-di(4-trifluoromethylphenyl)-1,3-dioxolanone
  参考文献：
  名称：

  Induction of Cholesteric Mesophases by Simple Cyclic Derivatives of p,p‘-Disubstituted 1,2-Diphenylethane-1,2-diols:  Importance of Shape and Polarizability Effects

  摘要：

  A systematic study of the cholesteric induction in nematic solvents (MBBA and E7) by some cyclic derivatives of unsubstituted and p,p'-disubstituted-1,2-diphenylethane-1, shows that the values of the twisting power are significantly dependent on the nature of the link connecting the two oxygen atoms and on the nature of the p,p'-substituents. This result has been interpreted considering that the nature of the bridge affects the overall molecular shape and the p,p'-substituents affect both the molecular polarizability and shape. This investigation points out that the polarizability of the solute and the solvent is the main parameter in determining the value of the twisting power while electrostatic arene-arene interactions contribute to a less extent. It has been also observed that solutes having the same structure and the same absolute configuration can induce cholesteric helix of opposite sign depending on the substituent on the aromatic ring. This finding indicates that configurational assignments by cholesteric induction are reliable only if high values of twisting power are measured.

  DOI：

  10.1021/jo990038y
• 作为产物：
  描述：

  (E)-1,2-双(4-(三氟甲基)苯基)乙烯 在 甲基磺酰胺 、 AD-mix-β 作用下， 以 水 、 叔丁醇 为溶剂， 反应 48.0h， 以67%的产率得到(1R,2R)-1,2-bis(4-(trifluoromethyl)phenyl)ethane-1,2-diol
  参考文献：
  名称：

  The modulation of face–face π–π interactions in Lewis acid catalysis

  摘要：

  The enantiomeric excess observed for the exo-adduct from the Lewis acid catalysed Diels-Alder reaction between cyclopentadiene and niethacrolein can be increased Lip to 21%, by simple modification of the electronics of the aromatic ring in a series of stilbene-derived diol ligands, suggesting that the proposed face-face pi-pi interaction between the catalyst and the dienophile can be modulated by altering the electron density on the aromatic ring. (C) 2005 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetlet.2005.01.086

文献信息

• Isothiourea-Catalysed Sequential Kinetic Resolution of Acyclic (±)-1,2-Diols
  作者：Siegfried Harrer、Mark D. Greenhalgh、Rifahath M. Neyyappadath、Andrew D. Smith

  DOI：10.1055/s-0037-1610721

  日期：2019.8

  The isothiourea-catalysed acylative kinetic resolution of a range of acyclic (±)-1,2-diols using 1 mol% of catalyst under operationally simple conditions is reported. Significantly, the bifunctional nature of (±)-1,2-diols was exploited in a sequential double kinetic resolution, in which both kinetic resolutions operate synergistically to provide access to highly enantioenriched products. The principles

  报告了在操作简单的条件下使用 1 mol% 催化剂对一系列无环 (±)-1,2-二醇进行异硫脲催化的酰化动力学拆分。值得注意的是，(±)-1,2-二醇的双功能特性在连续双动力学拆分中得到了利用，其中两种动力学拆分协同运作以提供对高度对映体富集的产品的访问。讨论了支持该过程的原理，并在模型系统中报告了各个动力学拆分步骤的选择性因素。
• Hydrogen Bonding-Assisted Enhancement of the Reaction Rate and Selectivity in the Kinetic Resolution of <i>d,l</i> -1,2-Diols with Chiral Nucleophilic Catalysts
  作者：Kazuki Fujii、Koichi Mitsudo、Hiroki Mandai、Seiji Suga

  DOI：10.1002/adsc.201700057

  日期：2017.8.17

  An extremely efficient acylative kinetic resolution of d,l‐1,2‐diols in the presence of only 0.5 mol% of binaphthyl‐based chiral N,N‐4‐dimethylaminopyridine was developed (selectivity factor of up to 180). Several key experiments revealed that hydrogen bonding between the tert‐alcohol unit(s) of the catalyst and the 1,2‐diol unit of the substrate is critical for accelerating the rate of monoacylation

  在仅0.5 mol％的联萘基手性N，N -4-二甲基氨基吡啶存在下，开发了一种极有效的d，l - 1,2-二醇的酰基动力学拆分方法（选择性因子高达180）。几个关键实验表明，催化剂的叔醇单元与底物的1,2-二醇单元之间的氢键键合对于加快单酰化速率和实现高对映选择性至关重要。该催化体系可广泛应用于涉及外消旋无环和环状1,2-二醇且具有高选择性因子的底物。d，l-氢安息香和反式的动力学拆分数克级（10 g）的1,2-环己二醇也具有较高的选择性并在中等反应条件下进行：（i）催化剂负载量极低（0.1 mol％）; （ii）容易达到的低反应温度（0°C）；（iii）高底物浓度（1.0 M）；（iv）反应时间短（30分钟）。
• Catalytic asymmetric dihydroxylation of substituted trans-stilbene derivatives: implications of the variation of enantioselectivities on the mechanism of OsO4 addition to olefins
  作者：Mariappan Periasamy、Sakilam Satish Kumar、N. Sampath Kumar

  DOI：10.1016/j.tetlet.2008.05.016

  日期：2008.7

  The OsO4 catalyzed asymmetric dihydroxylation of substituted trans-stilbene derivatives using 9-O-acetyldihydrocinchonidine as chiral ligand gives the corresponding diols with lower enantioselectivity in the case of substrates containing electron-donating and electron-withdrawing substituents. The Hammett correlations of the enantiomeric ratios exhibit non-linear plots, in accordance with the conclusion

  在含有给电子和吸电子取代基的底物的情况下，使用9- O-乙酰基二氢辛可尼定作为手性配体，OsO 4催化了取代的反式-二苯乙烯衍生物的不对称二羟基化反应，使相应的二醇具有较低的对映选择性。根据该反应涉及1，3-偶极型[3 + 2]环加成过渡态的结论，对映体比率的哈米特相关性显示非线性图。
• Horeau amplification in the sequential acylative kinetic resolution of (±)-1,2-diols and (±)-1,3-diols in flow
  作者：Arianna Brandolese、Mark D. Greenhalgh、Titouan Desrues、Xueyang Liu、Shen Qu、Cyril Bressy、Andrew D. Smith

  DOI：10.1039/d1ob00304f

  日期：——

  The sequential acylative kinetic resolution (KR) of C2-symmetric (±)-1,2-syn and (±)-1,3-anti-diols using a packed bed microreactor loaded with the polystyrene-supported isothiourea, HyperBTM, is demonstrated in flow. The sequential KRs of C2-symmetric (±)-1,2-syn and (±)-1,3-anti-diols exploits Horeau amplification, with each composed of two successive KR processes, with each substrate class significantly

  C 2 -对称 (±)-1,2- syn和 (±)-1,3-抗二醇的顺序酰化动力学拆分 (KR)使用装载有聚苯乙烯负载的异硫脲 HyperBTM 的填充床微反应器是流中表现出来。C 2 -对称 (±)-1,2- syn和 (±)-1,3- anti -diols的顺序KRs 利用 Horeau 放大，每个都由两个连续的 KR 过程组成，每个底物类别在每个 KR 过程的相对速率常数。优化C 2 -对称 (±)-1,2- syn和 (±)-1,3- anti的连续流动设置-二醇底物类别允许以高对映纯度和产率分离反应产物。除了C 2 -对称 (±)-1,2- syn和 (±)-1,3- anti -diols 的成功 KR 之外，将该过程应用于概念上更复杂的场景，包括证明了C 1 -对称 (±)-1,3-抗二醇，它涉及八个独立的速率常数。
• Enantioselective Pinacol Coupling of Aldehydes Mediated and Catalyzed by Chiral Titanium Complexes
  作者：Ahlem Bensari、Jean-Luc Renaud、Olivier Riant

  DOI：10.1021/ol016664a

  日期：2001.11.1

  Starting from easily available chiral Schiff bases, a straightforward synthesis of air-stable titanium(IV) complexes was devised. Asymmetric pinacol coupling of aromatic aldehydes mediated and catalyzed by the corresponding low valent complexes afforded the chiral diols with high yields and enantioselectivities up to 91%. [reaction: see text]

  从容易获得的手性席夫碱开始，设计了一种空气稳定的钛（IV）配合物的直接合成方法。由相应的低价络合物介导和催化的芳族醛的不对称频哪醇偶联提供了高收率和高达91％的对映选择性的手性二醇。[反应：看文字]