(S)-2-hydroxy-2-(3,4-methylenedioxyphenyl)acetonitrile | 151593-25-8

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 苯并间二氧杂环戊烯类
• 英文名称: (S)-2-hydroxy-2-(3,4-methylenedioxyphenyl)acetonitrile
• 英文别名: (2S)-2-(2H-1,3-benzodioxol-5-yl)-2-hydroxyacetonitrile；(2S)-2-(1,3-benzodioxol-5-yl)-2-hydroxyacetonitrile
• CAS: 151593-25-8
• 化学式: C₉H₇NO₃
• 分子量: 177.159
• InChiKey: JWZKLCWLXKKOLL-SSDOTTSWSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1
• 重原子数：
  13
• 可旋转键数：
  1
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.22
• 拓扑面积：
  62.5
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  (S)-2-hydroxy-2-(3,4-methylenedioxyphenyl)acetonitrile 、 乙酰氯 在 吡啶 作用下， 以 二氯甲烷 为溶剂， 生成 (S)-(+)-1-cyano-1-[3,4-(methylenedioxy)phenyl]methyl acetate
  参考文献：
  名称：

  双功能BINOLAM-AlCl与单功能BINOL-AlCl配合物催化的三甲基甲硅烷基氰化物对醛的对映选择性加成

  摘要：

  醛的高度对映选择性氰化是通过使用衍生自3,3'-双（二乙基氨基甲基）取代的联萘酚（BINOLAM）和氯化二甲基铝的双官能催化剂进行的。该添加物的范围很广，并且在甲苯中，在4ÅMS和三苯基氧化膦作为添加剂的情况下，在-20至-40°C的温度下效果最佳。的（[R ）-或（小号使用（当）-cyanohydrins结果小号或（ - ）- [R）-BINOLAM-AlCl配合物。有价值的配体可以通过简单的提取后处理进行回收，并在不损失效率的情况下进行回收（无论是化学产率还是立体化学产率）。该方法学适用于Shibasaki合成埃坡霉素A的过程。所有可将BINOLAM-AlCl TMSCN对醛选择性加成到醛中的证据都要求进行氢氰化反应，即在原位生成催化量的氰化氢。醛，然后进行O-甲硅烷基化。为了确定BINOLAM的碱性氨基的作用，对单官能的1,1'-联萘酚衍生的复合物BINOL-AlCl进行了比较研究。

  DOI：

  10.1016/j.tet.2004.06.137
• 作为产物：
  描述：

  sodium cyanide 、 胡椒醛 在 (S)-hydroxynitrile lyase 、 溶剂黄146 作用下， 以 水 、 异丙醇 为溶剂， 反应 96.0h， 生成 (S)-2-hydroxy-2-(3,4-methylenedioxyphenyl)acetonitrile
  参考文献：
  名称：

  A simple separation method for (S)-hydroxynitrile lyase from cassava and its application in asymmetric cyanohydrination

  摘要：

  Using an acetone precipitation method, crude (S)-hydroxynitrile lyase [(S)-MeHNL] was separated from Munihot esculenta (cassava) leaves, and used directly as biocatalyst to catalyze asymmetric cyanohydrination and produce cyanohydrins with enantiomeric purities (>= 90% ee) significantly greater than those previously reported. The use of a water/i-Pr2O system with an enzyme, NaCN, and appropriate amounts of acetic acid is crucial in improving the stereoselectivity of cyanohydrin formation by minimizing the non-enzymatic reaction and the racemization of the chiral products. The proposed isolation method for crude (S)-MeHNL has a high value because of its simplicity, and low cost as well as the high activity of the crude (S)-MeHNL. (C) 2013 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetasy.2013.03.015

文献信息

• (R)- and (S)-cyanohydrins using oxynitrilases in whole cells
  作者：Eero Kiljunen、Liisa T Kanerva

  DOI：10.1016/0957-4166(96)00116-4

  日期：1996.4

  Almond meal and Sorghum bicolor shoots were used as the sources of oxynitrilases for the preparation of a number (R)- and (S)-arylcyanohydrins, respectively, from the corresponding aldehydes in diisopropyl ether. Two different in situ methods were used to introduce hydrogen cyanide into the reaction mixture. In method 1, acetone cyanohydrin decomposes enzymatically and/or chemically to hydrogen cyanide

  杏仁粉和高粱双色芽被用作氧硝化酶的来源，分别从二异丙基醚中的相应醛中制备许多（R）-和（S）-芳基氰醇。使用两种不同的原位方法将氰化氢引入反应混合物中。在方法1中，丙酮氰醇通过酶和/或化学方式分解为氰化氢。在方法2中，氰化氢从二异丙醚中的溶液从反应容器的一个腔室中自由蒸发，最终到达另一个溶解在反应混合物中的区域。
• Purification and Characterization of A Novel (<i>R</i>)-Hydroxynitrile Lyase from<i>Eriobotrya japonica</i>(Loquat)
  作者：Techawaree UEATRONGCHIT、Ai KAYO、Hidenobu KOMEDA、Yasuhisa ASANO、Aran H-KITTIKUN

  DOI：10.1271/bbb.80023

  日期：2008.6.23

  A hydroxynitrile lyase was isolated and purified to homogeneity from seeds of Eriobotrya japonica (loquat). The final yield, of 36% with 49-fold purification, was obtained by 30–80% (NH4)2SO4 fractionation and column chromatography on DEAE-Toyopearl and Concanavalin A Sepharose 4B, which suggested the presence of a carbohydrate side chain. The purified enzyme was a monomer with a molecular mass of 72 kDa as determined by gel filtration, and 62.3 kDa as determined by SDS-gel electrophoresis. The N-terminal sequence is reported. The enzyme was a flavoprotein containing FAD as a prosthetic group, and it exhibited a K  m of 161 μm and a k  cat⁄K  m of 348 s−1 mm−1 for mandelonitrile. The optimum pH and temperature were pH 5.5 and 40 °C respectively. The enzyme showed excellent stability with regard to pH and temperature. Metal ions were not required for its activity, while activity was significantly inhibited by CuSO4, HgCl2, AgNO3, FeCl3, β-mercaptoethanol, iodoacetic acid, phenylmethylsulfonylfluoride, and diethylpyrocarbonate. The specificity constant (k  cat⁄K  m) of the enzyme was investigated for the first time using various aldehydes as substrates. The enzyme was active toward aromatic and aliphatic aldehydes, and showed a preference for smaller substrates over bulky one.

  从枇杷(Eriobotrya japonica)种子中分离并纯化出一种羟腈裂解酶，使其达到均一性。通过30-80%(NH4)2SO4分级分离和DEAE-Toyopearl和Concanavalin A Sepharose 4B柱层析，获得了最终产率为36%、纯化倍数为49倍的酶，这表明存在一个碳水化合物侧链。纯化的酶是一个单体，通过凝胶过滤测定的分子质量为72 kDa，通过SDS-凝胶电泳测定的分子质量为62.3 kDa。报道了N-末端序列。该酶是一种含FAD作为辅基的黄素蛋白，对扁桃腈的Km值为161 μm，kcat/Km值为348 s-1 mm-1。最适pH和温度分别为pH 5.5和40 °C。该酶在pH和温度方面表现出极佳的稳定性。金属离子对其活性不是必需的，而CuSO4、HgCl2、AgNO3、FeCl3、β-巯基乙醇、碘乙酸、苯甲磺酰氟和二乙基焦碳酸酯对其活性有显著抑制作用。首次使用各种醛作为底物研究了该酶的特异性常数(kcat/Km)。该酶对芳香族和脂肪族醛均具有活性，并且对较小的底物比庞大的底物表现出偏好性。
• Preparation of chiral cyanohydrins by an oxynitrilase-mediated transcyanation
  作者：Vassil I. Ognyanov、Violeta K. Datcheva、Keith S. Kyler

  DOI：10.1021/ja00018a042

  日期：1991.8

  The transcyanation of aromatic and aliphatic aldehydes 1 (RCHO) with acetone cyanohydrin is catalyzed by the enzyme D-oxynitrilase to afford (R)-cyanohydrins 2 (RCH(OH)CN). The biocatalytic method using acetone cyanohydrin gives products of high enantiomeric purity with better consistency than similar conditions using hydrogen cyanide as the cyanide source. The use of an ether-buffer biphasic solvent system is essential for producing products of optimum optical purity, but the solubility properties of the substrate have a pronounced effect on the enantiomeric purity of the final product. A discussion relating the solubility partition coefficient (log P) of a substrate to the enantiomeric purity of the product as a guide for predicting the outcome with new substrates is presented. Application of the method to the preparation of the following cyanohydrins is reported (R, ee): a, C6H5, 92% ee; b, 3,4-(CH2O2)C6H3, 90% ee; c, 2-(CH3O)C6H4, 96% ee; d, C6H5CH2, 88% ee; e, CH3SCH2CH2, 92% ee; f, CH3(CH2)5CH2, 92% ee; g, (CH3)3C, 92% ee; h, c-C6H11, 96% ee; i, CH3O2C(CH2)6CH2, 97% ee; j, (E,E)-CH3CH = CHCH = CH, 96% ee; k, (CH3)2C = CHCH2CH2C(CH3) = CH, 99% ee.
• Matthews, Barry R.; Jackson, W. Roy; Jayatilake, Gamini S., Australian Journal of Chemistry, 1988, vol. 41, # 11, p. 1697 - 1710
  作者：Matthews, Barry R.、Jackson, W. Roy、Jayatilake, Gamini S.、Wilshire, Colin、Jacobs, Howard A.

  DOI：——

  日期：——
• Foerster, Siegfried; Roos, Juergen; Effenberger, Franz, Angewandte Chemie, 1996, vol. 108, # 4, p. 493 - 494
  作者：Foerster, Siegfried、Roos, Juergen、Effenberger, Franz、Wajant, Harald、Sprauer, Achim

  DOI：——

  日期：——