(S)-3-hydroxy-2-methylene-3-phenylpropanenitrile

• 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)-3-hydroxy-2-methylene-3-phenylpropanenitrile
• 英文别名: (+)-2-[((hydroxy)phenyl)methyl]acrylonitrile；(S)-2-(hydroxy(phenyl)methyl)acrylonitrile；(S)-2-(hydroxyphenylmethyl)acrylonitrile；2-[(S)-hydroxy(phenyl)methyl]prop-2-enenitrile
• 化学式: C₁₀H₉NO
• 分子量: 159.188
• InChiKey: SBDMZDGNPLMNDF-SNVBAGLBSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.4
• 重原子数：
  12
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.1
• 拓扑面积：
  44
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (S)-3-hydroxy-2-methylene-3-phenylpropanenitrile 、 (R)-(+)-α-甲氧基-α-(三氟甲基)苯乙酸 在 4-二甲氨基吡啶 、 N,N'-二环己基碳二亚胺 作用下， 以 二氯甲烷 为溶剂， 反应 0.5h， 以82%的产率得到(R)-[(S)-2-cyano-1-phenylallyl]3,3,3-trifluoro-2-methoxy-2-phenylpropanoate
  参考文献：
  名称：

  Enzymatic kinetic resolution of Morita-Baylis-Hillman acetates

  摘要：

  Racemic Morita-Baylis-Hillman adducts derived from the reaction of acrylonitrile with benzaldehyde, cinnamaldehyde and hydrocinnamaldehyde have been successfully resolved by means of enzymatic kinetic resolution. The (+)-alcohol products were isolated with 94-97% ee after lipase-mediated enantios-elective hydrolysis of the corresponding acetates. Mosher's double derivatisation protocol was applied to these isolated products and the absolute configuration of the alcohols was found to be (S) for all three substrates. (C) 2017 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetasy.2017.08.001
• 作为产物：
  描述：

  苯丙腈,b-羟基-a-亚甲基- 在 4-二甲氨基吡啶 、 Amano AK lipase 、 三乙胺 作用下， 以 aq. phosphate buffer 、 二氯甲烷 为溶剂， 反应 19.5h， 生成 (S)-3-hydroxy-2-methylene-3-phenylpropanenitrile
  参考文献：
  名称：

  Enzymatic kinetic resolution of Morita-Baylis-Hillman acetates

  摘要：

  Racemic Morita-Baylis-Hillman adducts derived from the reaction of acrylonitrile with benzaldehyde, cinnamaldehyde and hydrocinnamaldehyde have been successfully resolved by means of enzymatic kinetic resolution. The (+)-alcohol products were isolated with 94-97% ee after lipase-mediated enantios-elective hydrolysis of the corresponding acetates. Mosher's double derivatisation protocol was applied to these isolated products and the absolute configuration of the alcohols was found to be (S) for all three substrates. (C) 2017 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetasy.2017.08.001

文献信息

• Substrate Evaluation of<i>Rhodococcus erythropolis</i>SET1, a Nitrile Hydrolysing Bacterium, Demonstrating Dual Activity Strongly Dependent on Nitrile Sub-Structure
  作者：Tracey M. Coady、Lee V. Coffey、Catherine O'Reilly、Claire M. Lennon

  DOI：10.1002/ejoc.201403201

  日期：2015.2

  Rhodococcus erythropolis SET1, a novel nitrile hydrolysing bacterial isolate, has been undertaken with 34 nitriles, 33 chiral and 1 prochiral. These substrates consist primarily of β-hydroxy nitriles with varying alkyl and aryl groups at the β position and containing in several compounds different substituents α to the nitrile. In the case of β-hydroxy nitriles without substitution at the α position

  红球菌 SET1 是一种新型腈水解细菌分离株，已使用 34 种腈、33 种手性和 1 种前手性进行了评估。这些底物主要由 β-羟基腈组成，在 β 位具有不同的烷基和芳基，并且在几种化合物中含有与腈不同的 α 取代基。在 α 位没有取代的 β-羟基腈的情况下，由于分离物的腈水解酶活性，酸是获得的主要产物，以及生物转化后回收的腈。出乎意料的是，当 β-羟基腈在该位置具有乙烯基时，发现酰胺是主要的水解产物。为了进一步探索这种行为，评估了在 α 位置包含吸电子基团的其他相关底物，在 SET1 存在下的生物转化过程中也观察到了酰胺。因此，这种新的分离物也证明了对似乎是底物依赖性的腈类的 NHaSE 活性。
• Cationic chiral surfactant based micelle-guided asymmetric Morita-Baylis-Hillman reaction
  作者：Bashir Ahmad Shairgojray、Aijaz Ahmad Dar、Bilal A. Bhat

  DOI：10.1016/j.catcom.2016.05.010

  日期：2016.8

  Cationic chiral surfactant (1R, 2S)-(-)-N-dodecyl-N-methylephedrinium bromide (DMEB) was utilized for the first time in inducing asymmetry to Morita-Baylis-Hillman reaction in aqueous medium. Proton NMR studies carried out to determine the locus of the reaction in micro-heterogeneous micellar environment, were found useful in proposing a plausible model for asymmetric induction. This work demonstrates that under such mild and nonhazardous reactions conditions, the reaction rates increase, good yields are favored and above all reasonable enantiomeric excesses are obtained. (C) 2016 Elsevier B.V. All rights reserved.
• Lewis Base Catalyzed Enantioselective Allylic Hydroxylation of Morita–Baylis–Hillman Carbonates with Water
  作者：Bo Zhu、Lin Yan、Yuanhang Pan、Richmond Lee、Hongjun Liu、Zhiqiang Han、Kuo-Wei Huang、Choon-Hong Tan、Zhiyong Jiang

  DOI：10.1021/jo201096e

  日期：2011.8.19

  A Lewis base catalyzed allylic hydroxylation of Morita-Baylis-Hillman (MBH) carbonates has been developed. Various chiral MBH alcohols can be synthesized in high yields (up to 99%) and excellent enantioselectivities (up to 94% ee). This is the first report using water as a nucleophile in asymmetric organocatalysis. The nucleophilic role of water has been verified using O-18-labeling experiments.
• Nonenzymatic Acylative Kinetic Resolution of Baylis−Hillman Adducts
  作者：Ciarán Ó Dálaigh、Stephen J. Connon

  DOI：10.1021/jo071223b

  日期：2007.8.31

  The first efficient nonenzymatic acylative kinetic resolution of Baylis-Hillman adducts is reported. Chiral pyridine catalyst 1a and an optimized analogue 1e are capable of promoting the synthetically useful enantioselective acylation (the efficiency of which is outstanding for sp(2)-sp(2) carbinol substrates, s = 3.5-13.1, ee up to 97%) of Baylis-Hillman adducts derived from recalcitrant precursors which are currently difficult to synthesize utilizing benchmark asymmetric Baylis-Hillman reaction catalyst technology. A novel one-pot synthesis-kinetic resolution process involving a DBU-catalyzed Baylis-Hillman reaction and subsequent 1e/DBU-mediated enantioselective acylation has also been developed.