(R)-4-乙氧基-α-甲基苯乙醇 | 225920-04-7

• 物质功能分类: 有机原料 - 醇、酚、酚醇类化合物及衍生物
• 分子结构分类: 有机化合物 - 苯类化合物 - 苯酚醚
• 中文名称: (R)-4-乙氧基-α-甲基苯乙醇
• 中文别名: (R)-1-(4-乙氧基苯基)乙醇
• 英文名称: (R)-(+)-1-(4-ethoxyphenyl) ethanol
• 英文别名: (1R)-1-(4-ethoxyphenyl)ethan-1-ol；(1R)-1-(4-ethoxyphenyl)ethanol
• CAS: 225920-04-7
• 化学式: C₁₀H₁₄O₂
• mdl: MFCD09863704
• 分子量: 166.22
• InChiKey: GKGQWBJLOYXULB-MRVPVSSYSA-N

物化性质

• 沸点：
  270.9±23.0 °C(Predicted)
• 密度：
  1.032±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.8
• 重原子数：
  12
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.4
• 拓扑面积：
  29.5
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  溶剂黄146 、 (R)-4-乙氧基-α-甲基苯乙醇 在 偶氮二甲酸二异丙酯 、 三苯基膦 作用下， 反应 24.0h， 生成 (S)-(-)-1-(4-乙氧基苯基)乙酸乙酯
  参考文献：
  名称：

  A green route to enantioenriched (S)-arylalkyl carbinols by deracemization via combined lipase alkaline-hydrolysis/Mitsunobu esterification

  摘要：

  Herein we report results of the chemoenzymatic deracemization of a range of secondary benzylic acetates 1a-9a via a sequence of hydrolysis with CAL-B lipase in non-conventional media, combined with esterification of the recovered alcohol according to the Mitsunobu protocol following an enzymatic kinetic resolution (KR). The KR of racemic acetates 1a-9a via an enzymatic hydrolysis, with CAL-B lipase and Na2CO3, in non-aqueous media was optimized and gave high selectivities (E >> 200) at good conversions (C >49%) for all of the substrates studied. This method competes well with the traditional one performed in a phosphate buffer solution. The deracemization using Mitsunobu inversion gave the (S)-acetates in moderate to excellent enantiomeric excess 75% < ee < 99%, in acceptable isolated yields 70% < yield < 89%, and with some variations according to the acetate structure. (C) 2013 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetasy.2013.01.020
• 作为产物：
  描述：

  (R)-1-(4-ethoxyphenyl)ethyl acetate 在 immobilized CALB lipase 、 氨 作用下， 以 异丙醚 为溶剂， 反应 12.0h， 生成 (R)-4-乙氧基-α-甲基苯乙醇
  参考文献：
  名称：

  A tandem and fully enzymatic procedure for the green resolution of chiral alcohols: acylation and deacylation in non-aqueous media

  摘要：

  A green and fully enzymatic procedure for the resolution of chiral alcohols through lipase/esterase-catalyzed acylation and subsequent lipase-catalyzed aminolysis using anhydrous ammonia was demonstrated. Both enantiomers can be obtained in high ee values (up to >99%) under ambient reaction conditions. The solvent and acyl donors can be recycled, and the enzyme can be reused for up to five times. (C) 2011 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetasy.2011.05.022

文献信息

• Reconstruction of the Catalytic Pocket and Enzyme-Substrate Interactions To Enhance the Catalytic Efficiency of a Short-Chain Dehydrogenase/Reductase
  作者：Aipeng Li、Lidan Ye、Xiaohong Yang、Bei Wang、Chengcheng Yang、Jiali Gu、Hongwei Yu

  DOI：10.1002/cctc.201600921

  日期：2016.10.20

  effect on the stereoselectivity. The increased steric repulsion and the C−H⋅⋅⋅π interaction involving the alkyl side chain of L153 and the phenyl ring of the substrate turned out to be crucial factors connected to the enhanced enzymatic activity. This provided new insight into the role of steric hindrance and non canonical interactions in protein engineering. Furthermore, the recombinant E. coli whole

  为了将短链脱氢酶/还原酶EbSDR8升级为合成抗Prelog手性醇的强大工具，通过重构催化口袋和酶-底物相互作用进行了合理的设计。所得变体显示出对一系列前手性酮的催化效率（k cat / K M；k cat =周转率，K M =米氏常数）显着提高，其中k cat / K M在某些情况下，其值比野生型EbSDR8高15倍以上。更重要的是，没有一个突变对立体选择性产生不利影响。事实证明，增加的空间排斥力和涉及L153的烷基侧链和底物的苯环的CH- H⋅⋅⋅π相互作用是与增强酶促活性有关的关键因素。这为空间位阻和非典型相互作用在蛋白质工程中的作用提供了新的见解。此外，重组大肠杆菌表达EbSDR8变体G94A / S153L的完整细胞成功催化了高浓度的2,2,2-三氟苯乙酮的还原。结果证明了合理设计的有效性以及所设计的变体在有效减少手性酮方面的适用性。
• CAL-B-Catalyzed Enantioselective Deacetylation of Some Benzylic Acetate Derivatives Via Alcoholysis in Non-aqueous Media
  作者：Amna Zaïdi、Mounia Merabet-Khelassi、Louisa Aribi-Zouioueche

  DOI：10.1007/s10562-014-1470-7

  日期：2015.4

  Abstract Enantioselective deacetylation of a set of benzylic acetates via alcoholysis catalyzed by Lipase B from Candida antarctica (CAL-B), under mild conditions is described. A systematic study allows to determine the appropriate combination nucleophile/organic solvent and also to explain the influence of these parameters on the enzymatic catalytic reaction. In all cases, (R)-alcohols are obtained

  摘要 描述了在温和条件下通过来自南极念珠菌 (CAL-B) 的脂肪酶 B 催化的醇解对一组苄基乙酸酯进行对映选择性脱乙酰化。系统研究可以确定合适的亲核试剂/有机溶剂组合，并解释这些参数对酶催化反应的影响。在所有情况下，在转化率 36 % < C < 48 %、选择性达到 E > 500 时，获得的 (R)-醇具有高 ee（高达 >99%）。酶促反应性受溶剂疏水性和亲核试剂的结构/性质。此外，CAL-B 允许在非水介质中的酯交换之间进行对映互补：醇解和乙酰化。图形摘要
• Green methodology for enzymatic hydrolysis of acetates in non-aqueous media via carbonate salts
  作者：Mounia Merabet-Khelassi、Zahia Houiene、Louisa Aribi-Zouioueche、Olivier Riant

  DOI：10.1016/j.tetasy.2012.06.001

  日期：2012.6

  Herein we report a new approach to enantiomerically enriched acetates using a lipase-catalyzed hydrolysis in non-aqueous media by alkaline carbonate salts. The use of sodium carbonate in the enzymatic hydrolysis with Candida antarctica lipase B (CAL-B) of racemic acetates shows a large enhancement of the reactivity and selectivity of this lipase. The role of the carbonate salts, the amount and the

  本文中，我们报告了一种新方法，可利用脂肪酶催化的非水介质中碱性碳酸盐在对映体上富集乙酸盐。在外消旋乙酸的南极假丝酵母脂肪酶B（CAL-B）的酶促水解中使用碳酸钠显示出该脂肪酶的反应性和选择性大大提高。研究了碳酸盐的作用，碱土金属的数量和性质对这种新途径的效率的影响。描述了在温和条件下通过酶促碳酸酯水解产生的乙酸酯1a – 9a的酶促动力学拆分。在所有情况下，所得到的醇和残留的乙酸盐都具有较高的ee值（高达> 99％），而选择性达到E。 > 500。
• Enantiocomplementary C–H bond hydroxylation through a dual-enzyme catalyzed one-pot two-step process
  作者：Jian Xu、Pan Ma、Qing-song Chen

  DOI：10.1039/d4nj02444c

  日期：——

  challenge. This study introduces a one-pot, two-step C–H bond hydroxylation process that integrates HRP-catalyzed oxidation and carbonyl reductase-catalyzed reduction for the enantiocomplementary synthesis of benzyl alcohols (up to 77% yield and 99% ee). This mild and operationally simple process provides an alternative approach to enantioselective benzylic hydroxylation.

  从烷基芳烃合成手性苯甲醇的对映选择性苄基氧化提出了挑战。本研究介绍了一种一锅两步 C-H 键羟基化工艺，该工艺集成了 HRP 催化氧化和羰基还原酶催化还原，用于对映互补合成苯甲醇（产率高达 77%，ee 高达 99%）。这种温和且操作简单的过程为对映选择性苄基羟基化提供了另一种方法。
• The Scope of Catalytic Asymmetric Hydroboration/Oxidation with Rhodium Complexes of 1,1′‐(2‐Diarylphosphino‐1‐naphthyl)isoquinolines
  作者：Henri Doucet、Elena Fernandez、Timothy P. Layzell、John M. Brown

  DOI：10.1002/(sici)1521-3765(19990401)5:4<1320::aid-chem1320>3.0.co;2-#

  日期：1999.4

  Preformed cationic Rh complexes of the title ligands are effective for the asymmetric hydroboration/oxidation of vinylarenes at ambient temperature. These vinylarenes may carry E- or Z-beta substituents but not a substituents. Enantiomer excesses of up to 97% can be obtained in the most favourable cases. The enantioselectivity is moderately sensitive to the structure of the ligand: the difurylphosphino ligand gave superior results for electron-poor styrenes and the diphenylphosphino ligand the best results for electron-rich reactants. Mechanistic aspects are discussed.