(1R,2S)-1,2-bis-(2-trifluoromethyl-phenyl)-ethane-1,2-diol | 916525-57-0

• 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,2S)-1,2-bis-(2-trifluoromethyl-phenyl)-ethane-1,2-diol
• 英文别名: meso-1,2-bis[2-(trifluoromethyl)phenyl]ethane-1,2-diol；(1R,2S)-1,2-bis[2-(trifluoromethyl)phenyl]ethane-1,2-diol
• CAS: 916525-57-0
• 化学式: C₁₆H₁₂F₆O₂
• 分子量: 350.26
• InChiKey: PBKAEYPBALHMCY-OKILXGFUSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.7
• 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：

  (1R,2S)-1,2-bis-(2-trifluoromethyl-phenyl)-ethane-1,2-diol 在 对甲苯磺酸一水合物 、 sodium hydride 作用下， 以 甲醇 、 二氯甲烷 、 N,N-二甲基甲酰胺 为溶剂， 反应 26.0h， 生成 (1R,2S)-2-(2-methylpropoxy)-1,2-bis[2-(trifluoromethyl)phenyl]ethanol
  参考文献：
  名称：

  Chiral linker. Part 3: Synthesis and evaluation of aryl substituted m-hydrobenzoins as solid supported open chain chiral auxiliaries for the diastereoselective reduction of α-keto esters

  摘要：

  Five partly novel aryl substituted m-hydrobenzoins were synthesized and the corresponding desymmetrized hydrobenzoin ethers evaluated as open chain chiral auxiliaries in the L-Selectride (R) mediated stereoselective reduction of phenylglyoxylates, resulting in de values of up to 91%. Two optimized auxiliary structures were immobilized on commercially available Wang-resin and applied as a reusable solid supported chiral auxiliary in the same type of reaction. (c) 2006 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetasy.2006.08.017
• 作为产物：
  描述：

  2-hydroxy-1,2-bis[2-(trifluoromethyl)phenyl]ethanone 在 sodium tetrahydroborate 作用下， 以 乙醇 为溶剂， 反应 3.0h， 以21%的产率得到(1R,2S)-1,2-bis-(2-trifluoromethyl-phenyl)-ethane-1,2-diol
  参考文献：
  名称：

  Chiral linker 5: scope and limitations of arylsubstituted m-hydrobenzoins as solid supported open chain chiral auxiliaries for diastereoselective syntheses

  摘要：

  The applicability of five aryl substituted m-hydrobenzoin ethers already tested in the L-Selectride (R) mediated stereoselective reduction of phenylglyoxylates as open chain chiral auxiliaries was further investigated via the alpha-alkylation of propionates, the addition of n-BuZnCl to phenylglyoxylates and the Diels-Alder reaction of acrylates with cyclopentadiene as model reactions. As up to 90% cle could be achieved in the solution phase, two optimized auxiliary structures were immobilized on commercially available Wang-resin and applied as a reusable solid supported chiral auxiliaries in the same type of reactions. (C) 2009 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetasy.2009.02.004

文献信息

• Enantioselective Pinacol Coupling of Aryl Aldehydes Catalyzed by Chiral Salan−Mo(IV) Complexes
  作者：Hongwei Yang、Hongsong Wang、Chengjian Zhu

  DOI：10.1021/jo701842r

  日期：2007.12.1

  Reported herein is the asymmetric pinacol coupling of aromatic aldehydes with chiral Salan−Mo(VI) dioxo complex as an effective precatalyst. Chiral diols were obtained with high diastereoselectivity and enantioselectivity up to 92/8 and 95%, respectively. The possible mechanism of the pinacol coupling reaction with the catalytic system was investigated. The X-ray crystal structure of the precatalyst

  本文报道的是芳香醛与手性Salan-Mo（VI）二氧杂配合物作为有效的预催化剂的不对称频哪醇偶联。获得的手性二醇的非对映选择性高，对映选择性分别高达92/8和95％。研究了频哪醇偶联反应与催化体系的可能机理。通过X射线光电子能谱研究确定了前催化剂Mo（L3）O 2的X射线晶体结构，并确认了中间体C的氧化态为+4。拟议的机制推测了反应的立体化学结果，并提出了E自由基偶联的工作模型，该模型解释了所偏爱的（S，d1异构体的S）-对映异构体。
• Photoinduced generation of ketyl radicals and application in C–C coupling withoutexternal photocatalyst
  作者：Yonggang Yan、Gang Li、Jiani Ma、Chao Wang、Jianliang Xiao、Dong Xue

  DOI：10.1039/d3gc00054k

  日期：——

  radicals, enabling a series of important reactions in synthetic chemistry, such as the reductive coupling of aldehydes, ketones, and imines, the allylation of aldehydes, the Barbier reaction, reductive arylation, and aldehyde–aniline coupling. We also present evidence to support the ketyl radicals being formed via photoinduced intermolecular electron transfer from the tertiary amine to aryl aldehydes.

  通过光氧化还原催化对羰基进行单电子还原能够产生羰基自由基，为构建 C-C 键提供了一个良性过程。然而，需要外部光催化剂。本文报道了光诱导羰基自由基的产生及其在C-C偶联中的应用，无需使用任何外部光催化剂。在叔胺存在下用紫光照射羰基会产生高反应性的羰基自由基，使合成化学中的一系列重要反应成为可能，如醛、酮和亚胺的还原偶联、醛的烯丙基化、Barbier 反应，还原芳基化和醛 - 苯胺偶联。我们还提供证据支持通过以下方式形成的羰基自由基从叔胺到芳基醛的光诱导分子间电子转移。
• Synthesis of three-dimensionally arranged bis-biphenol ligand on hexaaryl benzene scaffold and its application for cross-pinacol coupling reaction
  作者：Toru Amaya、Akihiro Miyasaka、Toshikazu Hirao

  DOI：10.1016/j.tetlet.2011.06.113

  日期：2011.8

  The three-dimensionally arranged bis-biphenol ligand on a hexaaryl benzene scaffold for a dinuclear complex was synthesized by the Diels-Alder addition-decarbonylation reaction as a key step. Its preliminary studies on the titanium-induced cross-pinacol coupling reaction were performed based on step-by-step activation of two different aldehydes. (C) 2011 Elsevier Ltd. All rights reserved.
• Chiral linker 5: scope and limitations of arylsubstituted m-hydrobenzoins as solid supported open chain chiral auxiliaries for diastereoselective syntheses
  作者：Joachim Broeker、Max Knollmueller、Peter Gaertner

  DOI：10.1016/j.tetasy.2009.02.004

  日期：2009.2

  The applicability of five aryl substituted m-hydrobenzoin ethers already tested in the L-Selectride (R) mediated stereoselective reduction of phenylglyoxylates as open chain chiral auxiliaries was further investigated via the alpha-alkylation of propionates, the addition of n-BuZnCl to phenylglyoxylates and the Diels-Alder reaction of acrylates with cyclopentadiene as model reactions. As up to 90% cle could be achieved in the solution phase, two optimized auxiliary structures were immobilized on commercially available Wang-resin and applied as a reusable solid supported chiral auxiliaries in the same type of reactions. (C) 2009 Elsevier Ltd. All rights reserved.
• Chiral linker. Part 3: Synthesis and evaluation of aryl substituted m-hydrobenzoins as solid supported open chain chiral auxiliaries for the diastereoselective reduction of α-keto esters
  作者：Joachim Broeker、Max Knollmueller、Peter Gaertner

  DOI：10.1016/j.tetasy.2006.08.017

  日期：2006.9

  Five partly novel aryl substituted m-hydrobenzoins were synthesized and the corresponding desymmetrized hydrobenzoin ethers evaluated as open chain chiral auxiliaries in the L-Selectride (R) mediated stereoselective reduction of phenylglyoxylates, resulting in de values of up to 91%. Two optimized auxiliary structures were immobilized on commercially available Wang-resin and applied as a reusable solid supported chiral auxiliary in the same type of reaction. (c) 2006 Elsevier Ltd. All rights reserved.