(R)-2,2,2-trifluoro-1-(2,4,6-trimethylphenyl)ethanol | 102626-53-9

• 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)-2,2,2-trifluoro-1-(2,4,6-trimethylphenyl)ethanol
• 英文别名: (R)-(-)-1-mesityl-2,2,2-trifluoroethanol；mesityl-2,2,2-trifluoroethanol；(1R)-2,2,2-trifluoro-1-(2,4,6-trimethylphenyl)ethan-1-ol；(1R)-2,2,2-trifluoro-1-(2,4,6-trimethylphenyl)ethanol
• CAS: 102626-53-9；131832-00-3
• 化学式: C₁₁H₁₃F₃O
• 分子量: 218.219
• InChiKey: FLVCXPCTCZOGJF-SNVBAGLBSA-N

物化性质

• 熔点：
  52-54 °C(Solv: hexane (110-54-3); ethyl ether (60-29-7))
• 沸点：
  273.9±40.0 °C(Predicted)
• 密度：
  1.174±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.3
• 重原子数：
  15
• 可旋转键数：
  1
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.45
• 拓扑面积：
  20.2
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  (R)-2,2,2-trifluoro-1-(2,4,6-trimethylphenyl)ethanol 在 正丁基锂 、 1,10-菲罗啉 、 二氯乙基铝 作用下， 反应 13.0h， 生成 bis[(1R)-2,2,2-trifluoro-1-(2,4,6-trimethylphenyl)ethyl] (1R,2R,3R,4S)-bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylate
  参考文献：
  名称：

  1-Mesityl-2,2,2-trifluoroethanol, an outstanding new chiral controller for catalyzed diels-alder reactions

  摘要：

  The R2AlCl-catalyzed Diels-Alder reactions of cyclopentadiene with the (R)-1-mesityl-2,2,2-trifluoroethyl esters of acrylic and fumaric acid proceed with > 97:3 diastereoselectivity.

  DOI：

  10.1016/0040-4039(91)80420-b
• 作为产物：
  描述：

  2-溴-1,3,5-三甲基苯 在 正丁基锂 、 oxazaborolidine 1 (R=n-Bu) 、 儿萘酚硼烷 作用下， 以 甲苯 为溶剂， 反应 42.5h， 生成 (R)-2,2,2-trifluoro-1-(2,4,6-trimethylphenyl)ethanol
  参考文献：
  名称：

  从非手性酮中合成对映体纯的仲甲醇非常有效和简单

  摘要：

  手性恶唑硼烷（1）催化还原酮的2，6和8提供了简单访问手性仲原醇3，7，和9以非常高的对映体纯度。

  DOI：

  10.1016/0040-4039(91)80419-7

文献信息

• Fine tuning of molecular and supramolecular properties of simple trianglimines – the role of the functional group
  作者：J. Gajewy、J. Szymkowiak、M. Kwit

  DOI：10.1039/c6ra06095a

  日期：——

  affected by the nature and chirality of the dopant. The hexaimine macrocycles after reduction of the CN imine bonds formed trianglamines – useful chiral ligands in stereoselective synthesis. The Zn–trianglamine complexes were employed as catalysts for asymmetric hydrosilylation of prochiral ketones, providing products of enantiomeric excess up to 98%. This remains the best result obtained for Zn–diamine

  容易从对映体纯的反式-1，2-二氨基环己烷和各种芳族二醛中获得的手性，三角形聚氮杂大环（trianglimines），其性质和取代方式不同。在满足所谓的对称规则的熵的热力学控制下，形成具有两个连接于芳基部分的给电子基团的高度对称的大环。相反，仅从2-硝基对苯二甲酸乙醛获得平凡的C 1对称性的动力学产物，而从2-甲氧基对苯二甲酸乙醛则得到C 3-和C 1的混合物。对称的大环形成。在实验/理论方法的基础上确定了影响大环形成机理的因素。大环的非对称结构是由环缩合过程中出现的对称中间体引起的。通过量子化学计算支持的实验性ECD和VCD方法研究了Trianglimines的手性。硝基取代的trianglimine似乎是在稳定的手性有机凝胶的极性介质中形成的一种简单的低分子量超级胶凝剂。凝胶的结构受掺杂剂的性质和手性的影响。C还原后的六亚胺大环N亚胺键形成trianglamines –在立体选择性合成
• Asymmetric hydrosilylation of ketones catalyzed by complexes formed from trans-diaminocyclohexane-based diamines and diethylzinc
  作者：Jadwiga Gajewy、Jacek Gawronski、Marcin Kwit

  DOI：10.1007/s00706-012-0754-0

  日期：2012.7

  Chiral acyclic and macrocyclic amines derived from trans-1,2-diaminocyclohexane in complexes with diethylzinc efficiently catalyze asymmetric hydrosilylation of aryl-alkyl and aryl-aryl ketones with enantiomeric excess of the product up to 86 %. A trianglamine ligand with a cyclic structure or the presence of an additional coordinating group increases the enantioselectivity of the reaction, in comparison

  摘要：由反式 1,2-二氨基环己烷衍生的手性无环胺和大环胺与二乙基锌形成络合物，可有效催化芳基烷基酮和芳基芳基酮的不对称氢化硅烷化，产物对映体过量高达 86%。与简单的无环N,N'-二苄基-1,2-二氨基环己烷配体的催化相比，具有环状结构或存在额外配位基团的三胺配体提高了反应的对映选择性。此外，还研究了多种醇和二醇对催化剂不对称活化的影响。图形概要：
• Convenient Enantioselective Hydrosilylation of Ketones Catalyzed by Zinc-Macrocyclic Oligoamine Complexes
  作者：Jadwiga Gajewy、Marcin Kwit、Jacek Gawroński

  DOI：10.1002/adsc.200800801

  日期：2009.5

  Abstractmagnified imageChiral macrocyclic tetra‐ and hexamine macrocycles derived from trans‐1,2‐diaminocyclohexane (DACH) in complexes with diethylzinc efficiently catalyze the asymmetric hydrosilylation of aryl alkyl ketones with enantiomeric excess of the product up to 89%. The cyclic structure of the trianglamine ligand increases the enantioselectivity of the reaction, in comparison to the catalysis with the acyclic N,N′‐dibenzyl‐DACH ligand. Density functional theory (DFT) computations on the structures of ligand‐zinc complexes and on the structures of these complexes with a coordinated acetophenone molecule allow us to rationalize the direction of the asymmetric induction of the hydrosilylation reaction as well as the superiority of the cyclic ligand compared to the acyclic one. This is the first example of asymmetric catalysis for the hydrosilylation reaction of ketones with the use of a readily available, inexpensive, and reusable macrocyclic trianglamine ligand.
• Enantioselective reduction of aryl trifluoromethyl ketones with BINAL-H. A preparation of 2,2,2-trifluoro-1-(9-anthryl)ethanol
  作者：J. Michael Chong、Eduardo K. Mar

  DOI：10.1021/jo00002a082

  日期：1991.1
• Enantioselective Reduction of Trifluoromethyl Ketones with Chiral Organomagnesium Amides (COMAs)
  作者：Kelvin H. Yong、J. Michael Chong

  DOI：10.1021/ol026901p

  日期：2002.11.1

  [GRAPHICS]Chiral organomagnesium amides (COMAs), readily prepared from dialkylmagnesiums and chiral secondary amines, can reduce trifluoromethyl ketones to form secondary alcohols with excellent enantioselectivities (up to 98:2 er) and chemical yields (typically >95% conversion, >85% isolated yields). These MPV-type reductions use an achiral hydride source, and the chiral amine is readily recovered.