(S)-3-羟基戊腈 | 199177-61-2

• 分子结构分类: 有机化合物 - 有机氧化合物
• 中文名称: (S)-3-羟基戊腈
• 英文名称: (S)-3-hydroxypentanenitrile
• 英文别名: Pentanenitrile, 3-hydroxy-, (3S)-；(3S)-3-hydroxypentanenitrile
• CAS: 199177-61-2
• 化学式: C₅H₉NO
• mdl: MFCD09027304
• 分子量: 99.1326
• InChiKey: FXHRDEQPODSZQL-YFKPBYRVSA-N

物化性质

• 沸点：
  227.9±13.0 °C(Predicted)
• 密度：
  0.968±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0.2
• 重原子数：
  7
• 可旋转键数：
  2
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.8
• 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-羟基戊腈 在 platinum(IV) oxide 咪唑 、 正丁基锂 、 氢气 、 二异丁基氢化铝 作用下， 以 乙醚 、 乙醇 、 二氯甲烷 、 N,N-二甲基甲酰胺 、 甲苯 为溶剂， -78.0~25.0 ℃ 、101.33 kPa 条件下， 反应 61.0h， 生成 (S)-(+)-3-辛醇
  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
• 作为产物：
  描述：

  (S)-1-cyanobutan-2-yl acetate 在 Pseudomonas ceracia lipase 、 水 作用下， 以 丙酮 为溶剂， 生成 (S)-3-羟基戊腈
  参考文献：
  名称：

  硫冠醚添加剂对脂肪酶催化反应的非对映选择性的影响：通过双酶促反应策略制备光学活性 3-羟基-2-甲基链烷腈

  摘要：

  已经研究了对脂肪酶催化水解 3-羟基-2-甲基-或 3-羟基-2-乙基链烷腈的乙酸酯的非对映选择性的累加效应。尽管观察到对映选择性的显着改变，但非对映选择性不受硫冠醚添加剂的影响。因此，脂肪酶催化反应的非对映选择性的起源明显不同于对映选择性的起源。基于这些结果，通过双酶促反应策略通过脂肪酶催化反应证明了光学活性 3-羟基-2-甲基戊腈和 3-羟基-2-甲基丁腈的简单制备。

  DOI：

  10.1246/bcsj.72.1589

文献信息

• Biocatalytic and Structural Properties of a Highly Engineered Halohydrin Dehalogenase
  作者：Marcus Schallmey、Robert J. Floor、Bernhard Hauer、Michael Breuer、Peter A. Jekel、Hein J. Wijma、Bauke W. Dijkstra、Dick B. Janssen

  DOI：10.1002/cbic.201300005

  日期：2013.5.10

  Synergistic mutations: A halohydrin dehalogenase with 37 mutations and improved catalytic properties for statin side chain synthesis has been biochemically characterized. Crystal structures with different ligands in the active site give insight into the way in which individual mutations contribute to enhanced stability and faster cyanolysis of epoxides and illustrate the importance of synergistic mutations

  协同突变：具有生化特性的卤化氢脱卤酶具有37个突变，并具有改善的他汀类侧链合成的催化性能。活性位点中具有不同配体的晶体结构使人们洞悉单个突变有助于增强环氧化物的稳定性和更快地氰基分解的方式，并说明了协同突变在定向进化中的重要性。
• Increased Enantioselectivity and Remarkable Acceleration of Lipase-Catalyzed Transesterification by Using an Imidazolium PEG–Alkyl Sulfate Ionic Liquid
  作者：Toshiyuki Itoh、Yuichi Matsushita、Yoshikazu Abe、Shi-hui Han、Shohei Wada、Shuichi Hayase、Motoi Kawatsura、Shigeomi Takai、Minoru Morimoto、Yoshihiko Hirose

  DOI：10.1002/chem.200601043

  日期：2006.12.13

  types of imidazolium salt ionic liquids were prepared derived from poly(oxyethylene)alkyl sulfate and used as an additive or coating material for lipase-catalyzed transesterification in an organic solvent. A remarkably increased enantioselectivity was obtained when the salt was added at 3-10 mol % versus substrate in the Burkholderia cepacia lipase (lipase PS-C)-catalyzed transesterification of 1-phenylethanol

  从聚（氧乙烯）烷基硫酸酯制备了几种类型的咪唑鎓盐离子液体，并用作在有机溶剂中脂肪酶催化的酯交换反应的添加剂或涂料。通过在二异丙醚或己烷溶剂体系中使用乙酸乙烯酯，在伯克霍尔德菌洋葱脂肪酶（脂肪酶PS-C）催化的1-苯基乙醇酯交换反应中，以相对于底物3-10 mol％的量添加盐时，可获得显着提高的对映选择性。尤其是，在iPr（2）O溶剂系统中，用脂肪酶PS进行离子液体涂覆可实现显着的加速，同时保持出色的对映选择性。对于某些具有出色对映选择性的底物，它达到了约500至1000倍的加速度。对于IL 1包被的假丝酵母念珠菌脂肪酶也观察到类似的加速。离子液体包被的脂肪酶PS的MALDI-TOF质谱实验表明，离子液体与脂肪酶蛋白结合。
• Remarkable Activation of an Enzyme by (<i>R</i>)-Pyrrolidine- Substituted Imidazolium Alkyl PEG Sulfate
  作者：Yoshikazu Abe、Takuya Hirakawa、Shino Nakajima、Nagisa Okano、Shuichi Hayase、Motoi Kawatsura、Yoshihiko Hirose、Toshiyuki Itoh

  DOI：10.1002/adsc.200800382

  日期：2008.9.5

  The chiral pyrrolidine-substituted imidazolium cetyl-PEG10-sulfate (D-ProMe) derived from D-proline worked as an excellent activating agent of Burkholderia cepacia lipase; it is particularly interesting that the D-isomer of the imidazolium salt worked better than the L-isomer. This suggests that the imidazolium cation group directly interacts with the enzyme protein and causes preferable modification

  衍生自D-脯氨酸的手性吡咯烷取代的咪唑十六烷基-PEG10-硫酸盐（D -ProMe）是伯克霍尔德酒原洋葱脂肪酶的极好活化剂。特别有趣的是，咪唑鎓盐的D-异构体比L-异构体的效果更好。这表明咪唑鎓阳离子基团直接与酶蛋白相互作用并且引起反应性的优选改变。
• A rational design of phosphonium salt type ionic liquids for ionic liquid coated-lipase catalyzed reaction
  作者：Yoshikazu Abe、Kazuhide Yoshiyama、Yusuke Yagi、Shuichi Hayase、Motoi Kawatsura、Toshiyuki Itoh

  DOI：10.1039/c0gc00151a

  日期：——

  A rational design of phosphonium ionic liquid for ionic liquid coated-lipase (IL1-PS)-catalyzed reaction has been investigated, and very rapid transesterification of secondary alcohols accomplished when IL1-PS was used as catalyst in 2-methoxyethoxymethyl(tri-n-butyl)phosphonium bis(trifluoromethanesulfonyl)amide ([P444MEM][NTf2]) as solvent while perfect enantioselectivity was maintaining. Increased Kcat value was suggested to be the most important factor in IL1-PS working the best in [P444MEM][NTf2] solvent.

  一种合理设计的磷阳离子液体用于涂层脂肪酶（IL1-PS）催化反应的研究表明，当使用IL1-PS作为催化剂时，在溶剂2-甲氧基乙氧基甲基（三正丁基）磷阳离子双（三氟甲磺酰）胺（[P444MEM][NTf2]）中，次级醇的酯转移反应非常快速，同时保持了完美的对映选择性。研究表明，Kcat值的增加被认为是IL1-PS在[P444MEM][NTf2]溶剂中表现最佳的最重要因素。
• Enantioselective Ring Opening of Epoxides with Cyanide Catalysed by Halohydrin Dehalogenases: A New Approach to Non-Racemic β-Hydroxy Nitriles
  作者：Maja Majerić Elenkov、Bernhard Hauer、Dick B. Janssen

  DOI：10.1002/adsc.200505333

  日期：2006.3

  Halohydrin dehalogenases (HheA, HheB and HheC) were found to efficiently catalyse a carbon-carbon bond forming reaction between terminal aliphatic epoxides and cyanide, yielding β-hydroxy nitriles. With all three enzymes nucleophilic ring opening of epoxides proceeds with high regioselectivity to the β-carbon atom. Activity, enantioselectivity and enantiopreference depend on the type of enzyme and

  发现卤代醇脱卤素酶（HheA，HheB和HheC）可有效催化末端脂肪族环氧化物与氰化物之间的碳-碳键形成反应，生成β-羟基腈。通过所有这三种酶，环氧化物的亲核开环以对β-碳原子的高区域选择性进行。活性，对映选择性和对映选择性取决于酶的类型和底物结构。发现HheC在测试的酶中具有最高的选择性。对单取代环氧化物的对映选择性从中等到高（E = 5–106）变化，而2,2-二取代环氧化物的拆分以非常高的对映选择性（E= 141和200）。结果表明，卤代醇脱卤酶可能成为从外消旋环氧化物容易地制备对映纯β-羟基腈的有吸引力的催化剂。