(S)-1-(3-chlorophenyl)ethyl acetate | 1103679-61-3

• 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: (S)-1-(3-chlorophenyl)ethyl acetate
• 英文别名: (S)-1-(3-chlorophenyl)ethanol acetate；[(1S)-1-(3-chlorophenyl)ethyl] acetate
• CAS: 1103679-61-3
• 化学式: C₁₀H₁₁ClO₂
• 分子量: 198.649
• InChiKey: MHPGGMAHRYXWQV-ZETCQYMHSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.6
• 重原子数：
  13
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.3
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为产物：
  描述：

  m-Chloro-α-acetoxystyrol 在 bis(1,5-cyclooctadiene)rhodium(I) tetrafluoroborate 、 C₄₁H₄₂N₃O₃P 、 氢气 作用下， 以 1,2-二氯乙烷 为溶剂， -20.0 ℃ 、500.01 kPa 条件下， 反应 10.0h， 生成 (S)-1-(3-chlorophenyl)ethyl acetate
  参考文献：
  名称：

  Rh（I）/ DpenPhos催化烯醇酯和（E）-3-氰基-5-甲基己-3-烯酸钾的不对称氢化

  摘要：

  一类模块化手性单齿亚磷酰胺的Rh（I）络合物对于带有α-芳基或α-烷基的烯醇酯的不对称氢化反应非常有效，从而可以提供高对映选择性（87-95％ee）的相应氢化产物。活动（周转数最多10,000）。这些配体还显示出在Rh（I）催化的（E）-3-氰基-5-甲基己基-3-烯酸酯的钾盐的Rh（I）催化的不对称氢化中有效，从而得到相应的产物（CI-1008的前体），并具有高达95％的ee，并且可以完成底物的完全转化。

  DOI：

  10.1016/j.tet.2012.05.096

文献信息

• Highly efficient dynamic kinetic resolution of secondary aromatic alcohols with low-cost and easily available acid resins as racemization catalysts
  作者：Yongmei Cheng、Gang Xu、Jianping Wu、Chensheng Zhang、Lirong Yang

  DOI：10.1016/j.tetlet.2010.02.152

  日期：2010.4

  A new and efficient dynamic kinetic resolution (DKR) process of secondary aromatic alcohols was developed with acid resins as racemization catalysts. Acid resin CD8604 was shown to have excellent racemization activity and good biocompatibility. When employing CD8604 and complex acyl donors as racemization catalyst and acyl donor, respectively, enantiomerically pure aromatic acetate was obtained with

  以酸性树脂为外消旋催化剂，开发了一种新型高效的仲芳族醇动力学动力学拆分方法。酸性树脂CD8604被证明具有出色的外消旋活性和良好的生物相容性。当分别使用CD8604和复杂的酰基给体作为外消旋催化剂和酰基给体时，通过DKR工艺可获得对映体纯的芳族乙酸酯，且收率和ee值极佳。值得注意的是，该系统可以重复使用10次以上，而产量和ee值的损失很小。
• CALB Immobilized onto Magnetic Nanoparticles for Efficient Kinetic Resolution of Racemic Secondary Alcohols: Long-Term Stability and Reusability
  作者：Xiu Xing、Jun-Qi Jia、Jing-Fan Zhang、Zi-Wen Zhou、Jun Li、Na Wang、Xiao-Qi Yu

  DOI：10.3390/molecules24030490

  日期：——

  immobilization of lipase and resolution of racemic 1-phenylethanol were investigated. Under optimal conditions, esters could be obtained with conversion of 50%, enantiomeric excess of product (eep) > 99%, enantiomeric excess of substrate (ees) > 99%, and enantiomeric ratio (E) > 1000. The magnetic CALB CLEAs were successfully used for enzymatic kinetic resolution of fifteen secondary alcohols. Compared with Novozym

  在这项研究中，开发并研究了南极假丝酵母脂肪酶B磁性交联酶聚集体的固定化策略。通过常规的共沉淀制备磁性颗粒。用3-氨基丙基三乙氧基硅烷（APTES）对磁性纳米粒子进行改性，以获得表面氨基官能化的磁性纳米粒子（APTES⁻Fe3 O 3）作为固定材料。戊二醛用作交联剂以使CALB与APTES⁻Fe₃O₃共价结合。研究了固定化脂肪酶和拆分外消旋1-苯基乙醇的最佳条件。在最佳条件下，可以以50％的转化率，产物的对映体过量（eep）> 99％，底物的对映体过量（ee）> 99％和对映体比率（E）> 1000获得酯。磁性CALB CLEAs已成功用于15种仲醇的酶动力学拆分。与Novozym 435相比，CALB CLEA磁性对大多数底物表现出更好的对映选择性。在48小时的反应周期中，将磁性CALB CLEA重复使用10次后，转化率仍大于49％。ee和eep都接近99％。此外，在-20℃下保存90天后，催化活性和对映选择性几乎没有降低。
• Stereochemistry and Mechanism of Enzymatic and Non-Enzymatic Hydrolysis of Benzylic<i>sec</i>-Sulfate Esters
  作者：Michael Toesch、Markus Schober、Rolf Breinbauer、Kurt Faber

  DOI：10.1002/ejoc.201402211

  日期：2014.6

  The substrate scope of inverting alkylsulfatase Pisa1 was extended towards benzylic sec-sulfate esters by suppression of competing non-enzymatic autohydrolysis by addition of dimethyl sulfoxide as co-solvent. Detailed investigation of the mechanism of autohydrolysis in 18O-labeled buffer by using an enantiopure sec-benzylic sulfate ester as substrate revealed that from the three possible pathways (i)

  通过添加二甲基亚砜作为助溶剂，抑制竞争性非酶自水解作用，将烷基硫酸酯酶Pisa1转化的底物范围扩展至苄基仲硫酸酯。以对映体纯的仲苄基硫酸酯为底物，在18O标记的缓冲液中自动水解机理的详细研究表明，从三个可能的途径（i）[SN-] [OH-]的SN2型亲核攻击在苄基碳上的转化代表：主要途径，（ii）导致消旋化的平面苄基碳正离子的SN1型形成是次要事件，并且（iii）在检测极限处发生了对硫的SN2型亲核攻击的保留。通过分析间位取代基的哈米特常数解释所获得的数据。
• Separation of enantiopure m-substituted 1-phenylethanols in high space-time yield using Bacillus subtilis esterase
  作者：Gao-Wei Zheng、Xu-Yun Liu、Zhi-Jun Zhang、Ping Tian、Guo-Qiang Lin、Jian-He Xu

  DOI：10.1039/c3ra41999a

  日期：——

  A recombinant Bacillus subtilis esterase (BsE) expressed in E. coli was found to exhibit excellent enantioselectivity (E was always greater than 100) towards m-substituted 1-phenylethanol acetates in the enantioselective hydrolysis reaction. An explanation for the high enantioselectivity observed towards these substrates was provided by molecular modeling. Moreover, the BsE also showed strong tolerance towards a high concentration of m-substituted 1-phenylethanol acetates (up to 1 M). Based on these excellent catalytic properties of BsE, a kind of m-substituted 1-phenylethanols, (R)-1-(3-chlorophenyl)ethanol, was efficiently synthesized in space-time yield of 920 g per L per day and 97% ee, indicating that the BsE was considered as a potentially ideal and promising biocatalyst for large-scale production of optically active m-substituted 1-phenylethanols.

  研究发现，在大肠杆菌中表达的重组枯草芽孢杆菌酯酶（BsE）在对映选择性水解反应中对 m-取代的 1-苯基乙醇乙酸酯表现出极好的对映选择性（E 始终大于 100）。分子模型为观察到的对这些底物的高对映选择性提供了解释。此外，BsE 还对高浓度的间取代 1-苯基乙醇乙酸酯（高达 1 M）表现出很强的耐受性。基于 BsE 的这些优异催化特性，一种间代 1-苯基乙醇--(R)-1-(3-氯苯基)乙醇被高效合成，时空产率为 920 克/升/天，ee 为 97%，这表明 BsE 被认为是大规模生产具有光学活性的间代 1-苯基乙醇的一种潜在的理想和有前途的生物催化剂。
• Baeyer–Villiger monooxygenase-catalyzed kinetic resolution of racemic α-alkyl benzyl ketones: enzymatic synthesis of α-alkyl benzylketones and α-alkyl benzylesters
  作者：Cristina Rodríguez、Gonzalo de Gonzalo、Daniel E. Torres Pazmiño、Marco W. Fraaije、Vicente Gotor

  DOI：10.1016/j.tetasy.2009.03.018

  日期：2009.6

  The application of three BVMOs for the enantioselective oxidation of 3-phenylbutan-2-ones with different substituents in the aromatic moiety is described. By choosing the appropriate biocatalyst and substrate combination, chiral ketones and esters can be obtained with excellent enantiopurities. This methodology could also be applied to the resolution of racemic alpha-alkyl benzylketones with longer alkyl chains as well as with two substituted alpha-substituted benzylacetones. A kinetic analysis revealed that the BVMOs studied effectively convert all tested compounds showing that the enzymes are tolerant towards the substrate structure while being highly enantioselective. These properties render BVMOs as valuable biocatalysts for the preparation of compounds with high interest in organic synthesis. (C) 2009 Elsevier Ltd. All rights reserved.