(R)-α-methyl-4-methoxybenzyl butyrate

• 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)-α-methyl-4-methoxybenzyl butyrate
• 英文别名: [(1R)-1-(4-methoxyphenyl)ethyl] butanoate
• 化学式: C₁₃H₁₈O₃
• 分子量: 222.284
• InChiKey: DQZASWBIXLZDSR-SNVBAGLBSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.8
• 重原子数：
  16
• 可旋转键数：
  6
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.46
• 拓扑面积：
  35.5
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为产物：
  描述：

  正丁酸乙烯酯 、 4-甲氧基-α-甲基苯甲醇 以 甲苯 为溶剂， 反应 19.0h， 生成 (S)-1-(4-methoxyphenyl)ethyl butyrate 、 (R)-α-methyl-4-methoxybenzyl butyrate
  参考文献：
  名称：

  Biocatalysis in Organic Synthesis. 9. Highly Enantioselective Kinetic Resolution of Secondary Alcohols Catalyzed by Acylase.¹

  摘要：

  发现了来自阿斯pergillus物种的酶酰化酶 I (AA-I) 的一种新催化活性。尽管该酶之前仅用于水解 N-酰基氨基酸，但我们发现它是使用乙烯基酯作为酰基供体进行转酯化反应的高效催化剂。该方法已应用于多种次级醇的动力学分辨。

  DOI：

  10.1055/s-1997-796

文献信息

• Removal of the acyl donor residue allows the use of simple alkyl esters as acyl donors for the dynamic kinetic resolution of secondary alcohols
  作者：Gerard K.M. Verzijl、Johannes G. de Vries、Quirinus B. Broxterman

  DOI：10.1016/j.tetasy.2005.02.028

  日期：2005.5

  dynamic kinetic resolution of secondary alcohols using a lipase and a ruthenium catalyst as developed by Bäckvall required some improvements to make it suitable for its use in an industrial process. The use of p-chlorophenyl acetate as acyl donor is not desirable in view of the toxicity of the side product. We herein report that simple alkyl esters can be used as acyl donors if the alcohol or ketone residue

  Bäckvall开发的使用脂肪酶和钌催化剂的仲醇动态动力学拆分方法需要进行一些改进，以使其适合工业过程使用。p的使用考虑到副产物的毒性，不希望使用乙酸-氯苯酯作为酰基供体。我们在本文中报道，如果在反应过程中连续除去在酶促酰化过程中形成的醇或酮残基，则可以将简单的烷基酯用作酰基供体。酮的添加加快了外消旋过程，使我们减少了酶和钌催化剂的用量。探索了该方法的范围，并找到了合适范围的酰基供体。使用丁酸异丙酯或苯乙酸甲酯作为酰基供体，使各种苄醇和脂肪醇反应，在大多数情况下，酯的收率> 95％，ee分离为99％。此外，
• Efficient dynamic kinetic resolution of secondary alcohols with a novel tetrafluorosuccinato ruthenium complex
  作者：Sjoerd F.G.M. van Nispen、Jeroen van Buijtenen、Jef A.J.M. Vekemans、Jan Meuldijk、Lumbertus A. Hulshof

  DOI：10.1016/j.tetasy.2006.08.003

  日期：2006.9

  Dynamic kinetic resolution (DKR) of a series of secondary alcohols has been conducted with a novel dinuclear ruthenium complex, bearing tetrafluorosuccinate and (rac)-BINAP ligands as the racemization catalyst. Novozym 435 has been used as the enzyme, and isopropyl butyrate as the acyl donor. Five substrates underwent DKR successfully: an aliphatic and an aromatic secondary alcohol, an aromatic alcohol

  已经用新型的双核钌配合物进行了一系列仲醇的动态动力学拆分（DKR），该配合物带有四氟琥珀酸酯和（rac）-BINAP配体作为外消旋催化剂。已将Novozym 435用作酶，并将丁酸异丙酯用作酰基供体。五个基材成功进行了DKR：脂族和芳族仲醇，在苯环上带有吸电子取代基的芳族醇，在环上带有给电子取代基的芳族醇和杂芳族仲醇。催化剂在70°C时表现最佳。通常，相对于底物，用0.1mol％的外消旋催化剂，反应在1天内达到完全转化。对应于底物的酮的添加稳定了活性Ru络合物，因此增加了反应速率。
• Combinatorial Library Based Engineering of<i>Candida antarctica</i>Lipase A for Enantioselective Transacylation of<i>sec</i>-Alcohols in Organic Solvent
  作者：Ylva Wikmark、Maria Svedendahl Humble、Jan-E. Bäckvall

  DOI：10.1002/anie.201410675

  日期：2015.3.27

  A method for determining lipase enantioselectivity in the transacylation of sec‐alcohols in organic solvent was developed. The method was applied to a model library of Candida antarctica lipase A (CalA) variants for improved enantioselectivity (E values) in the kinetic resolution of 1‐phenylethanol in isooctane. A focused combinatorial gene library simultaneously targeting seven positions in the enzyme

  开发了一种测定有机溶剂中仲醇转酰基反应中脂肪酶对映选择性的方法。该方法应用于南极假丝酵母脂肪酶 A (CalA) 变体模型库，以提高 异辛烷中 1-苯基乙醇的动力学拆分的对映选择性（ E值）。设计了同时靶向酶活性位点七个位置的集中组合基因库。通过组氨酸标签（His 6标签）将酶变体固定在镍包被的 96 孔微量滴定板上，筛选异辛烷中 1-苯基乙醇的转酰基作用，并通过 GC 进行分析。双突变体 Y93L/L367I 显示出最高的对映选择性。该酶变体的E 值为 100 ( R )，比野生型 CalA ( E = 3) 有了显着改进。该变体还对测试的其他仲醇表现出高至优异的对映选择性。
• Resolution of ( <i>R,S</i> )‐1‐(4‐methoxyphenyl)ethanol by lipase‐catalyzed stereoselective transesterification and the process optimization
  作者：Bingbing He、Fengci Tang、Chenrui Sun、Jiahao Su、Bingcheng Wu、Yan Chen、Yuquan Xiao、Panliang Zhang、Kewen Tang

  DOI：10.1002/chir.23402

  日期：2022.2

  An efficient lipase-catalyzed stereoselective transesterification reaction system was established for resolution of 1-(4-methoxyphenyl)ethanol (MOPE) enantiomers. A series of lipases were tested and compared. The immobilized lipase Novozym 40086 is selected as the best choice. The effects of organic solvent, acyl donor, time and temperature on substrate conversion (c), and optical purity of the remaining

  建立了一种高效的脂肪酶催化立体选择性酯交换反应体系，用于拆分 1-(4-甲氧基苯基)乙醇 (MOPE) 对映体。测试和比较了一系列脂肪酶。固定化脂肪酶 Novozym 40086 被选为最佳选择。研究了有机溶剂、酰基供体、时间和温度对底物转化率（c）和剩余底物光学纯度（ee S）的影响。采用响应面法和中心复合设计来评估一些重要因素的影响并优化过程。在包括n溶剂在内的优化条件下-己烷，乙酸乙烯酯的酰基供体，温度35℃，底物摩尔比1:6，酶用量20mg，反应时间2.5h，ee S为99.87%，c为56.71%。烷烃溶剂和固定化酶的使用、温和的反应条件和缩短的反应时间使该体系在工业应用中具有广阔的应用前景。
• (<i>S</i>)-Selective Dynamic Kinetic Resolution of Secondary Alcohols by the Combination of Subtilisin and an Aminocyclopentadienylruthenium Complex as the Catalysts
  作者：Mahn-Joo Kim、Yong Il Chung、Yoon Kyung Choi、Han Ki Lee、Daeho Kim、Jaiwook Park

  DOI：10.1021/ja036766r

  日期：2003.9.1

  A new procedure for the dynamic kinetic resolution (DKR) of racemic alcohols into single enantiomers is described. This procedure employs surfactant-treated subtilisin as an (S)-selective resolving catalyst and an aminocyclopentadienylruthenium complex as a racemizing catalyst. The DKR is performed best in the presence of an acyl donor such as trifluoroethyl butyrate in THF at room temperature. Eight simple secondary alcohols have been efficiently resolved with high optical purities and good yields. The subtilisin-based DKR is complementary in stereoselectivity to its lipase-based counterpart. For an acyl-carrying alcohol, both subtilisin- and lipase-based DKRs have proceeded equally well to give a pair of enantiomeric products (>99.5% ee each) with opposite optical rotations in high yields (94-95%).