3-phenylglutaronitrile | 78533-73-0

• 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: 3-phenylglutaronitrile
• 英文别名: 3-Phenylpentanedinitrile
• CAS: 78533-73-0
• 化学式: C₁₁H₁₀N₂
• 分子量: 170.214
• InChiKey: PTYUGKRGFBYREI-UHFFFAOYSA-N

物化性质

• 熔点：
  26 °C
• 沸点：
  207.5-208.5 °C(Press: 12 Torr)
• 密度：
  1.08210 g/cm3

计算性质

• 辛醇/水分配系数(LogP)：
  1.4
• 重原子数：
  13
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.27
• 拓扑面积：
  47.6
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  3-phenylglutaronitrile 在 Rhodococcus sp. AJ₂₇₀ cells 、 氯甲酸乙酯 、 三乙胺 作用下， 以 phosphate buffer 、 丙酮 为溶剂， 反应 31.5h， 生成 methyl N-[(2R)-3-cyano-2-phenylpropyl]carbamate
  参考文献：
  名称：

  Enzymatic desymmetrization of 3-alkyl- and 3-arylglutaronitriles, a simple and convenient approach to optically active 4-amino-3-phenylbutanoic acids

  摘要：

  The enantioselective hydrolysis of 3-alkyl- and 3-arylglutaronitriles catalyzed by Rhodococcus sp. AJ270 cells, afforded the corresponding (S)-3-substituted 4-cyanobutanoic acids with low to moderate enantiomeric purities. Additives such as acetone were found to significantly enhance the enantioselectivity of the desymmetrization, giving enantiomeric excesses of up to 95%. The synthetic potential of the homochiral product was also demonstrated by the preparation of optically active (R)- and (S)-4-amino-3-phenylbutanoic acids. (C) 2002 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0957-4166(02)00028-9
• 作为产物：
  描述：

  肉桂腈 、 乙腈 在 四乙基氟化铵水合物 作用下， 反应 0.17h， 以80%的产率得到3-phenylglutaronitrile
  参考文献：
  名称：

  Bellamy, Anthony J.; Kerr, John B.; McGregor, CChristopher J., Journal of the Chemical Society. Perkin transactions II, 1982, p. 161 - 168

  摘要：

  DOI：

文献信息

• Nitrilase from rhodococcus rhodochrous ncimb 11216
  申请人：——

  公开号：US20030157672A1

  公开（公告）日：2003-08-21

  The invention relates to nucleic acid sequences which code for a polypeptide having nitrilase activity, to nucleic acid constructs comprising the nucleic acid sequences, and to vectors comprising the nucleic acid sequences or the nucleic acid constructs. The invention further relates to amino acid sequences which are encoded by the nucleic acid sequences, and to microorganisms comprising the nucleic acid sequences, the nucleic acid constructs or vectors comprising the nucleic acid sequences or the nucleic acid constructs. The invention additionally relates to an enzymatic process for preparing carboxylic acids from the corresponding nitrites.

  这项发明涉及编码具有腈酶活性的多肽的核酸序列，包括包含该核酸序列的核酸构建物，以及包含该核酸序列或核酸构建物的载体。该发明还涉及由该核酸序列编码的氨基酸序列，以及包含该核酸序列、核酸构建物或包含该核酸序列或核酸构建物的载体的微生物。此外，该发明还涉及一种从相应的亚硝酸盐制备羧酸的酶法过程。
• Biocatalytic Desymmetrization of Prochiral 3-Aryl and 3-Arylmethyl Glutaramides: Different Remote Substituent Effect on Catalytic Efficiency and Enantioselectivity
  作者：Yu-Fei Ao、Li-Bin Zhang、Qi-Qiang Wang、De-Xian Wang、Mei-Xiang Wang

  DOI：10.1002/adsc.201800956

  日期：2018.12.3

  efficiently afforded 3‐substituted glutaric acid monoamides in up to 95% yield and >99.5% ee. Even far away from the reaction site, the substituents on the aryl still have a significant effect on the catalytic activity and enantioselectivity and different remote substituent effect was observed for the two types of substrates. The synthetic application of biocatalytic desymmetrization was demonstrated by

  在30°C下于中性磷酸盐缓冲液中用含酰胺酶的红球菌红球菌AJ270微生物全细胞催化剂催化，一系列前手性3-芳基和3-芳基甲基戊二酰胺的不对称水解有效地提供了3-取代的戊二酸单酰胺，收率高达95％和> 99.5％ee。甚至远离反应位点，芳基上的取代基仍然对催化活性和对映选择性具有显着影响，并且对于两种类型的底物观察到不同的远程取代基效果。获得的对映纯（R）-3-取代的4-氨基甲酰基丁酸产物轻松转化为手性二氢喹啉酮和δ证明了生物催化脱对称的合成应用内酯化合物。
• Electrochemical Reduction of Cinnamonitrile in the Presence of Carbon Dioxide: Synthesis of Cyano- and Phenyl-Substituted Propionic Acids
  作者：Huan Wang、Mei-Yu Lin、Kai Zhang、Su-Jiao Li、Jia-Xing Lu

  DOI：10.1071/ch08092

  日期：——

  Cyano- and phenyl-substituted propionic acids were synthesized simply and efficiently by electrocarboxylation of cinnamonitrile in undivided cells using the non-noble metal nickel as cathode and magnesium as the anode. The radical anion generated by the electroreduction of cinnamonitrile in the absence of CO2 is involved in several competitive reactions that lead to the formation of linear hydrodimers, cyclic hydrodimers, saturated dihydro products, and glutaronitrile derivatives. While under 101.325 kPa of CO2, the electrocarboxylation could easily be carried out in the absence of additional catalysts, and with good yield (84.8%). The influence of various synthetic parameters, such as the nature of the electrode, the working potential, the concentration, and the temperature, on the electrocarboxylation reaction was investigated.

  在以非贵金属镍为阴极、镁为阳极的非分裂电池中，通过对肉桂腈进行电羧化，简单而高效地合成了氰基和苯基取代的丙酸。在没有二氧化碳的情况下，肉桂腈电还原产生的自由基阴离子参与了几个竞争反应，从而形成线性氢二聚体、环状氢二聚体、饱和二氢产物和戊二腈衍生物。在二氧化碳压力为 101.325 千帕的条件下，电羧化反应可以在不使用额外催化剂的情况下轻松进行，而且产率很高（84.8%）。研究还探讨了电极性质、工作电位、浓度和温度等各种合成参数对电羧化反应的影响。
• Biocatalytic desymmetrization of 3-substituted glutaronitriles by nitrilases. A convenient chemoenzymatic access to optically active (S)-Pregabalin and (R)-Baclofen
  作者：YiTao Duan、PeiYuan Yao、Jie Ren、Chao Han、Qian Li、Jing Yuan、JinHui Feng、QiaQing Wu、DunMing Zhu

  DOI：10.1007/s11426-014-5139-2

  日期：2014.8

  prochiral 3-substituted glutaronitriles offers a new approach to access (S)-Pregabalin and (R)-Baclofen. A number of nitrilases from diverse sources were screened with 3-isobutylglutaronitriles (1a) or 3-(4′-chlorophenyl)glutaronitriles (1b) as the substrate. Some nitrilases were found to catalyze the desymmetric hydrolysis of 1a and 1b to form optically active 3-(cyanomethyl)-5-methylhexanoic acid (2a)

  前手性3-取代的戊二腈的去对称化提供了一种新的获取（S）-普瑞巴林和（R）-巴氯芬的方法。以3-异丁基戊二腈（1a）或3-（4'-氯苯基）戊二腈（1b）为底物，筛选了多种来源的腈水解酶。发现一些腈水解酶催化1a和1b的不对称水解，形成具有高对映异构体的光学活性3-（氰基甲基）-5-甲基己酸（2a）和3-（4'-氯苯基）-4-氰基丁酸（2b）。 excesse（EE）， 分别。使用传统的化学水解无法实现这一点。其中，AtNIT3生成（R）-2b，而BjNIT6402和HsNIT生成具有高转化率和ee值的相反的（S）-对映体。不仅腈水解酶对这些3-取代的戊二腈显示出不同的活性和立体选择性，底物的3-取代基对酶的活性和立体选择性也有很大的影响。（S）-2a和（S）-2b制备高产和ee分别使用BjNIT6402和HsNIT作为生物催化剂的数值。（的一个直接的Curtius重排小号- ）2A和（小号）
• Improving the catalytic efficiency and stereoselectivity of a nitrilase from <i>Synechocystis</i> sp. PCC6803 by semi-rational engineering en route to chiral γ-amino acids
  作者：Shanshan Yu、Peiyuan Yao、Jinlong Li、Jinhui Feng、Qiaqing Wu、Dunming Zhu

  DOI：10.1039/c8cy02455c

  日期：——

  3-substituted 4-cyanobutanoic acid offers an attractive approach to access chiral β-substituted γ-amino acids, an important moiety in pharmaceuticals. In this study, we employed enzyme-substrate docking and alanine scanning to determine the key amino acid residues which have a positive effect on the activity and stereoselectivity of a nitrilase from Synechocystis sp. PCC6803 (SsNIT). Then, site-saturation mutagenesis

  腈水解酶催化的3-取代的戊二腈脱对称为旋光的3-取代的4-氰基丁酸提供了一种吸引人的方法，可用于制备手性β-取代的γ-氨基酸，这是药物中的重要组成部分。在这项研究中，我们采用了酶-底物对接和丙氨酸扫描来确定关键氨基酸残基，这些残基对Synychocystis sp。的腈水解酶的活性和立体选择性具有积极的影响。PCC6803（不锈钢NIT）。然后，进行正氨基酸残基（H141，P194，M197，I201和F202）的位点饱和诱变和组合诱变，并用经鉴定，高活性和立体选择性可用于3-取代的戊二腈的脱对称化反应，以提供高达488 g L -1 d -1的高时空生产率的（S）-3-取代-4-氰基丁酸。分子计算表明，酶活性的提高可能是由于底物结合腔的扩大。有趣的是，同时提高了立体选择性。