(S)-2-hydroxy-2-phenylpropanenitrile | 174849-24-2

• 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)-2-hydroxy-2-phenylpropanenitrile
• 英文别名: (2S)-2-hydroxy-2-phenylpropanenitrile
• CAS: 174849-24-2
• 化学式: C₉H₉NO
• 分子量: 147.177
• InChiKey: NGLPDXCYIUHTNP-SECBINFHSA-N

物化性质

• 沸点：
  291.1±20.0 °C(Predicted)
• 密度：
  1.127±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.2
• 重原子数：
  11
• 可旋转键数：
  1
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.22
• 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：

  N,O-双(三甲基硅烷基)三氟乙酰胺 、 (S)-2-hydroxy-2-phenylpropanenitrile 在 吡啶 、 三氟乙酸酐 作用下， 以 二氯甲烷 为溶剂， 生成 (S)-2-trimethylsiloxy-2-phenyl propionitrile
  参考文献：
  名称：

  菜Man中羟基腈裂解酶合成脂肪族和α-卤代酮氰醇

  摘要：

  研究了来自Manihot esculenta的羟腈裂解酶对酮底物的潜力。据观察，脂族链的长度是脂族非支链酮转化的关键参数。较小的底物容易被高对映体选择物转化，但是链长的延长导致酶活性的显着降低。对于许多卤代，在此尤其是氟化的苯乙酮衍生物，已经合成了具有良好至中等对映选择性的相应的氰醇。

  DOI：

  10.1002/cctc.201300965
• 作为产物：
  描述：

  2-hydroxy-2-phenylpropionitrile 生成 (S)-2-hydroxy-2-phenylpropanenitrile
  参考文献：
  名称：

  Approach to(R)- and (S)-ketone cyanohydrins using almond and apple meal as the source of (R)-oxynitrilase

  摘要：

  The synthesis of aliphatic and aromatic (R)-ketone cyanohydrins through the addition of hydrogen cyanide to the corresponding ketones and the synthesis of the (S)-enantiomers through the kinetic resolution of racemic ketone cyanohydrins has been studied in the presence of almond or apple meal. Substrate tolerance of the (R)-oxynitrilases towards ketones ((RRC)-R-1-C-2=O) is highly restricted compared to that of structurally similar aldehydes, reactivity following the order of H>Me much greater than Et for R-2. In the case of aromatic methyl ketones reactivity difference (C6H5 much greater than p-Me-C6H4 for R-1) is notable. (C) 1997 Elsevier Science Ltd.

  DOI：

  10.1016/s0957-4166(97)00110-9

文献信息

• Enantioselective Cyanosilylation of Ketones with Lithium(I) Dicyanotrimethylsilicate(IV) Catalyzed by a Chiral Lithium(I) Phosphoryl Phenoxide
  作者：Manabu Hatano、Katsuya Yamakawa、Tomoaki Kawai、Takahiro Horibe、Kazuaki Ishihara

  DOI：10.1002/anie.201510682

  日期：2016.3.14

  A highly enantioselective cyanosilylation of ketones was developed by using a chiral lithium(I) phosphoryl phenoxide aqua complex as an acid/base cooperative catalyst. The pentacoordinate silicate generated in situ from Me3SiCN/LiCN acts as an extremely reactive cyano reagent. Described is a 30 gram scale reaction and the synthesis of the key precursor to (+)‐13‐hydroxyisocyclocelabenzine.

  通过使用手性锂（I）磷酰苯氧基水合络合物作为酸/碱协同催化剂，开发了酮的高度对映选择性氰基硅烷化产品。由Me 3 SiCN / LiCN原位生成的五配位硅酸盐是一种极易反应的氰基试剂。描述了一个30克规模的反应和（+）-13-羟基异环celabenzine的关键前体的合成。
• 13C NMR as a general tool for the assignment of absolute configuration
  作者：Iria Louzao、José Manuel Seco、Emilio Quiñoá、Ricardo Riguera

  DOI：10.1039/c0cc02774j

  日期：——

  (13)C NMR, alone or in combination with (1)H NMR, allows the assignment of the absolute configuration of chiral alcohols, amines, carboxylic acids, thiols, cyanohydrins, sec,sec-diols and sec,sec-aminoalcohols, derivatized with appropriate chiral auxiliaries. This extends the assignment possibilities of NMR to fully deuterated and to nonproton containing compounds.

  （13）C NMR单独或与（1）H NMR结合使用，可以确定衍生化的手性醇，胺，羧酸，硫醇，氰醇，仲，仲二醇和仲，仲氨基醇的绝对构型与适当的手性助剂。这将NMR的赋值可能性扩展到了完全氘代和不含质子的化合物。
• Enzyme catalysed formation of (S)-cyanohydrins derived from aldehydes and ketones in a biphasic solvent system
  作者：Herfried Griengl、Norbert Klempier、Peter Pöchlauer、Michael Schmidt、Nongyuan Shi、Antonina A Zabelinskaja-Mackova

  DOI：10.1016/s0040-4020(98)00901-6

  日期：1998.11

  By employing a vigorously stirred two phase system aqueous buffer/organic solvent and using the hydroxynitrile lyase from Hevea brasiliensis as biocatalyst enantiopure (S)-cyanohydrins from aliphatic, unsaturated, aromatic and heteroaromatic aldehydes and methyl alkyl and methyl phenyl ketones are obtained in high yield and in general 98–99% enantiomeric excess.

  通过使用剧烈搅拌的两相系统水性缓冲液/有机溶剂，并使用巴西橡胶树的羟基腈裂解酶作为生物催化剂，对映体纯（S）-氰醇从脂肪族，不饱和，芳香族和杂芳香族醛以及甲基烷基和甲基苯基酮中获得通常对映体过量98–99％。
• Cross-Linked Aggregates of the Hydroxynitrile Lyase fromManihot esculenta: Highly Active and Robust Biocatalysts
  作者：Andrzej Chmura、Geert M. van der Kraan、Filip Kielar、Luuk M. van Langen、Fred van Rantwijk、Roger A. Sheldon

  DOI：10.1002/adsc.200606140

  日期：2006.8

  The precipitation and cross-linking into CLEAs of the hydroxynitrile lyase (E.C. 4.1.2.10) from Manihot esculenta was investigated and an optimized procedure, which involved precipitation with (NH4)2SO4, was developed. It was found that a fast (photometric) assay severely underestimated the activity recovery in the CLEA due to rate-limiting diffusion, whereas in a synthetic assay the activity recovery

  研究了Manihot esculenta的羟腈裂解酶（EC 4.1.2.10）的沉淀和交联到CLEA中，并开发了涉及用（NH 4）2 SO 4沉淀的优化程序。发现由于限速扩散，快速（光度）测定法严重低估了CLEA中的活性恢复，而在合成测定法中，活性恢复率高达起始活性的93％。CLEA用于微水介质中各种醛和酮的氢氰化，即使在没有反应性底物的条件下，非酶促背景反应也可忽略不计。
• Hydroxynitrile Lyase in Organic Solvent-Free Systems to Overcome Thermodynamic Limitations
  作者：Jan von Langermann、Annett Mell、Eckhard Paetzold、Thomas Daußmann、Udo Kragl

  DOI：10.1002/adsc.200700016

  日期：2007.6.4

  active ketone cyanohydrins by using organic solvent-free systems has been investigated. Therefore, substrates with known unfavorable results within hydroxynitrile lyase-catalyzed reactions were selected for the determination of limitations and bottlenecks in ketone cyanohydrin synthesis. The highly (S)-selective hydroxynitrile lyase from Manihot esculenta (MeHNL) has been chosen for the conversion

  已经研究了通过使用无有机溶剂的体系克服光学活性的酮氰醇合成中的热力学限制。因此，选择在羟腈裂解酶催化的反应中具有已知不利结果的底物，以确定酮氰醇合成中的局限性和瓶颈。已经选择了来自Manihot esculenta（Me HNL）的高度（S）选择性羟腈裂解酶来转化苯乙酮和相应的衍生物，它们是与其他几种羟腈裂解酶也仅表现出低转化率的底物。在优化的反应条件下，使用无有机溶剂的系统，转化率高达99.0 ee，转化率高达78％获得（S）。最后，合成了5mL具有98.5％ee（S）的对映体过量的（S）-苯乙酮氰醇。