(R)-2-cyano-1-phenylethyl acetate | 198561-42-1

• 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-cyano-1-phenylethyl acetate
• 英文别名: (R)-3-acetyloxy-3-phenylpropanenitrile；(I(2)R)-I(2)-(Acetyloxy)benzenepropanenitrile；[(1R)-2-cyano-1-phenylethyl] acetate
• CAS: 198561-42-1
• 化学式: C₁₁H₁₁NO₂
• 分子量: 189.214
• InChiKey: IOINVUDAFYPKGX-LLVKDONJSA-N

物化性质

• 熔点：
  121-124 °C
• 沸点：
  327.9±30.0 °C(Predicted)
• 密度：
  1.117±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.3
• 重原子数：
  14
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.27
• 拓扑面积：
  50.1
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (R)-2-cyano-1-phenylethyl acetate 在 lithium hydroxide 作用下， 以 甲醇 为溶剂， 生成 肉桂腈
  参考文献：
  名称：

  β-羟基腈高效脂肪酶催化的动力学拆分和动态动力学拆分。绝对构型的校正和向手性β-羟基酸和γ-氨基醇的转化

  摘要：

  β-羟基腈1的化学酶动力学动力学拆分已使用南极假丝酵母脂肪酶B和钌催化剂进行。使用氢源以动态动力学拆分抑制酮的形成以良好的产率和高的对映选择性产生相应的乙酸酯2。结果表明，钌催化剂和酶在单独的反应中使用时可以循环使用。我们还报告了从1和2制备各种对映体纯的β-羟基酸衍生物和γ-氨基醇的情况。后一化合物也用于建立1和2的正确绝对构型。

  DOI：

  10.1002/1615-4169(200210)344:9<947::aid-adsc947>3.0.co;2-z
• 作为产物：
  描述：

  3-羟基-3-苯基丙腈正离子 在 1,4,8,11-四硫杂环十四烷 、 Lipase PS 作用下， 以 吡啶 、 二氯甲烷 、 水 、 丙酮 为溶剂， 反应 81.0h， 生成 (R)-2-cyano-1-phenylethyl acetate
  参考文献：
  名称：

  Thiacrown Ether Technology in Lipase-Catalyzed Reaction:  Scope and Limitation for Preparing Optically Active 3-Hydroxyalkanenitriles and Application to Insect Pheromone Synthesis

  摘要：

  Both reaction rate and enantioselectivity in Pseudomonas cepacia lipase (PCL)-catalyzed hydrolysis of 3-hydroxyalkanenitrile acetates were significantly changed by the addition of catalytic amounts of thiacrown ether (1,4,8,11-tetrathiacyclotetradecane). Although the-reaction rate of various nitriles was accelerated, the enantioselectivity greatly depended on the nature of the substrate. Among 10 substrates tested, thiacrown ether offered highest enantioselectivity in PCL-catalyzed hydrolysis of 1-(cyanomethyl)propyl acetate. Forty or more times this crown ether, molarity based on the enzyme, was required to attain an acceptably high reaction rate and enantioselectivity. Applying this technology, we succeeded in synthesizing the optically pure attractant pheromone of ant Myrmica scabrinodis (A), (R)-3-octanol and its antipode of (S)-isomer in good overall yields.

  DOI：

  10.1021/jo971288m

文献信息

• Combined Ruthenium(II) and Lipase Catalysis for Efficient Dynamic Kinetic Resolution of Secondary Alcohols. Insight into the Racemization Mechanism
  作者：Belén Martín-Matute、Michaela Edin、Krisztián Bogár、F. Betül Kaynak、Jan-E. Bäckvall

  DOI：10.1021/ja051576x

  日期：2005.6.1

  Pentaphenylcyclopentadienyl ruthenium complexes (3) are excellent catalysts for the racemization of secondary alcohols at ambient temperature. The combination of this process with enzymatic resolution of the alcohols results in a highly efficient synthesis of enantiomerically pure acetates at room temperature with short reaction times for most substrates. This new reaction was applied to a wide range

  五苯基环戊二烯基钌配合物 (3) 是室温下仲醇外消旋化的极好催化剂。该过程与醇的酶促拆分相结合，可以在室温下高效合成对映异构纯的乙酸酯，大多数底​​物的反应时间都很短。这种新反应适用于包括杂芳族醇在内的多种官能化醇，对于后者中的许多醇，首次通过动态动力学拆分 (DKR) 有效制备了对映纯乙酸酯。制备并研究了不同取代的环戊二烯基钌配合物作为醇外消旋化的催化剂。发现五芳基取代的环戊二烯基配合物是外消旋化的高效催化剂。用烷基取代芳基之一大大减慢了外消旋化过程。氢化钌 eta(5)-Ph(5)CpRu(CO)(2)H (8) 催化 (S)-1-苯基乙醇外消旋化的研究表明外消旋化发生在钌的配位范围内催化剂。在对甲苯基甲基酮（1 当量）存在下进行的 (S)-1-苯基乙醇外消旋化中缺乏酮交换支持这一结论，这产生 <1% 的 1-(对甲苯基)乙醇. 氯化钌和碘化物配合物 3a 和 3c 以及氢化钌配合物 8
• Al(OTf)3 as a highly efficient catalyst for the rapid acetylation of alcohols, phenols and thiophenols under solvent-free conditions
  作者：Ahmed Kamal、M. Naseer A. Khan、K. Srinivasa Reddy、Y.V.V. Srikanth、T. Krishnaji

  DOI：10.1016/j.tetlet.2007.03.162

  日期：2007.5

  Aluminium triflate (0.01–0.1 mol %) was found to be an efficient catalyst for the acylation of alcohols, phenols, thiols and sugars with acetic anhydride in high yields under solvent-free conditions in a short reaction time at room temperature. Racemization of optically active alcohols and epimerization of sugars were not observed. The acylation efficacy of various acyl donors was also investigated

  三氟甲磺酸铝（0.01–0.1 mol％）被发现是在室温下短时间内无溶剂条件下高产率地用乙酸酐酰化醇，酚，硫醇和糖的有效催化剂。没有观察到旋光性醇的消旋化和糖的差向异构化。还研究了各种酰基供体的酰化效力。
• Chemoenzymatic synthesis2 of both enantiomers of fluoxetine, tomoxetine and nisoxetine: lipase-catalyzed resolution of 3-aryl-3-hydroxypropanenitriles
  作者：Ahmed Kamal、G.B.Ramesh Khanna、R. Ramu

  DOI：10.1016/s0957-4166(02)00537-2

  日期：2002.9

  transesterification process in hydrophobic solvents (diisopropyl ether, toluene and hexane) enhanced the reaction rate drastically and gave optimal yields with high enantioselectivity (>99%). Moreover, enantiopure 3-hydroxy-3-phenylpropanenitrile products have been converted via enantioconvergent routes into the (R)- and (S)-enantiomers of the important anti-depressants fluoxetine, tomoxetine, nisoxetine and norfluoxetine

  （±）-3-羟基-3-苯基丙腈的简便制备方法是通过在乙醇水溶液中用NaCN开环氧化苯乙烯。随后通过脂肪酶介导的酯交换反应动力学分离该物质，得到S-醇和R-乙酸酯具有出色的收率和高对映选择性，尤其是对于脂肪酶PS-C'Amano'II而言。还研究了溶剂和脂肪酶固定化的作用。有趣的是，在疏水性溶剂（二异丙基醚，甲苯和己烷）的酯交换过程中使用固定化脂肪酶可大大提高反应速率，并以高对映选择性（> 99％）获得最佳收率。此外，对映体纯的3-羟基-3-苯基丙腈产物已通过对映收敛途径转化为重要的抗抑郁药氟西汀，托莫西汀，尼索西汀和去氟西汀的（R）-和（S）-对映体。
• Efficient Lipase-Catalyzed Kinetic Resolution and Dynamic Kinetic Resolution of β-Hydroxy Nitriles. A Route to Useful Precursors for γ-Amino Alcohols
  作者：Oscar Pàmies、Jan-E. Bäckvall

  DOI：10.1002/1615-4169(200108)343:6/7<726::aid-adsc726>3.3.co;2-5

  日期：2001.8
• Study of the enantioselectivity of the CAL-B-catalysed transesterification of α-substituted α-propylmethanols and α-substituted benzyl alcohols
  作者：Eduardo Garcı́a-Urdiales、Francisca Rebolledo、Vicente Gotor

  DOI：10.1016/s0957-4166(01)00532-8

  日期：2001.11

  A study of the enantioselectivity exhibited by the lipase B from Candida antarctica in the transesterification of different alpha-substituted alpha-propylmethanols with vinyl acetate is shown. The best results are obtained when the large-sized (L) substituent of the alcohol is either a phenyl group or more especially a cyclohexyl group, although the reaction rates are lower than when linear or slightly branched groups are present. It is also found that ramification at the beta-position of the L substituent has a deleterious effect on both lipase activity and enantioselectivity. Moreover, some alpha-substituted benzyl alcohols bearing medium-sized (M) substituents larger than an ethyl and smaller than a propyl group are resolved by means of this methodology with moderate-good enantioselectivities (E=46-57) and similar reaction rates. (C) 2002 Elsevier Science Ltd. All rights reserved.