(E)-ethyl 3-cyanobut-2-enoate | 6330-35-4

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 脂肪酰基
• 英文名称: (E)-ethyl 3-cyanobut-2-enoate
• 英文别名: 3-cyano-cis-crotonic acid ethyl ester；3-Cyan-cis-crotonsaeure-aethylester；Mesaconsaeure-α-aethylester-β-nitril；ethyl (E)-3-cyanobut-2-enoate
• CAS: 6330-35-4
• 化学式: C₇H₉NO₂
• 分子量: 139.154
• InChiKey: ZRKOIZAQWIGYPW-GQCTYLIASA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.8
• 重原子数：
  10
• 可旋转键数：
  3
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.43
• 拓扑面积：
  50.1
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (E)-ethyl 3-cyanobut-2-enoate 在 葡萄糖 、 Old Yellow Enzyme-2 、 重水 、 还原型辅酶Ⅰ 作用下， 以 aq. phosphate buffer 、 异丙醇 为溶剂， 反应 24.0h， 以99%的产率得到
  参考文献：
  名称：

  Rationalisation of the stereochemical outcome of ene-reductase-mediated bioreduction of α,β-difunctionalised alkenes

  摘要：

  The OYE1-3-mediated reductions of some alpha,beta-difunctionalised alkenes, showing on the double bond a nitrile and ester group, are submitted to a careful stereochemical analysis, in order to identify which of the two electron-withdrawing groups (EWGs) is responsible for the activation of the C=C double bond towards reduction and for establishing hydrogen bond interactions within the binding pocket of the enzymes. The results show that for most of these substrates the activating EWG is the CN moiety linked to the prostereogenic olefinic carbon atom. The final stereochemical outcome can be explained through the empirical model which has been recently developed for difunctionalised alkenes activated by carbonyl/carboxyl containing EWGs.In a single case the activation is due to the COOR group linked to the less substituted olefinic carbon atom: an alternative empirical model is established for this kind of substrates, taking into consideration the OYE-catalysed reductions of beta,beta'-disubstituted-a-monofunctionalised alkenes. (C) 2014 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.molcatb.2013.12.020
• 作为产物：
  描述：

  乙酰乙酸乙酯 在 吡啶 、 氯化亚砜 、 水 作用下， 以 二甲基亚砜 为溶剂， 生成 (E)-ethyl 3-cyanobut-2-enoate
  参考文献：
  名称：

  Rationalisation of the stereochemical outcome of ene-reductase-mediated bioreduction of α,β-difunctionalised alkenes

  摘要：

  The OYE1-3-mediated reductions of some alpha,beta-difunctionalised alkenes, showing on the double bond a nitrile and ester group, are submitted to a careful stereochemical analysis, in order to identify which of the two electron-withdrawing groups (EWGs) is responsible for the activation of the C=C double bond towards reduction and for establishing hydrogen bond interactions within the binding pocket of the enzymes. The results show that for most of these substrates the activating EWG is the CN moiety linked to the prostereogenic olefinic carbon atom. The final stereochemical outcome can be explained through the empirical model which has been recently developed for difunctionalised alkenes activated by carbonyl/carboxyl containing EWGs.In a single case the activation is due to the COOR group linked to the less substituted olefinic carbon atom: an alternative empirical model is established for this kind of substrates, taking into consideration the OYE-catalysed reductions of beta,beta'-disubstituted-a-monofunctionalised alkenes. (C) 2014 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.molcatb.2013.12.020

文献信息

• Mander’s Reagent for the Deoxycyanation of β-Diketones: A Direct Synthesis of Oxoalkenenitriles
  作者：J. Armando Lujan-Montelongo、Alicia E. Cruz-Jiménez、Jeferson B. Mateus-Ruiz、Carolina Silva-Cuevas

  DOI：10.1055/a-1809-6545

  日期：2022.6

  Ethyl cyanoformate and methyl cyanoformate (Mander’s reagent) are both routinely used to perform C-selective ketone alkoxycarbonylations. Interestingly, both reagents were found to yield oxoalkenenitriles through an unprecedented deoxycyanation of 1,3-dicarbonyl compounds (e.g., 2-methylcyclohexane-1,3-dione). Although this method is not general, this is the first time that both Mander’s reagent and

  氰基甲酸乙酯和氰基甲酸甲酯（曼德试剂）都经常用于进行 C-选择性酮烷氧基羰基化。有趣的是，发现这两种试剂都可以通过 1,3-二羰基化合物（例如 2-甲基环己烷-1,3-二酮）的前所未有的脱氧氰化产生氧代烯腈。虽然这种方法并不通用，但这是首次将 Mander 试剂和氰基甲酸乙酯用于 1,3-二羰基化合物的脱氧氰化，以制备合成有用的氧代烯烃腈。讨论了对本方法的底物范围的限制。
• Nickel-catalysed regio- and stereoselective hydrocyanation of alkynoates and its mechanistic insights proposed by DFT calculations
  作者：Shigeru Arai、Koichi Nakazawa、Xiao-Fei Yang、Masaya Nakajima、Shinji Harada、Atsushi Nishida

  DOI：10.1039/d4ob00380b

  日期：——

  We have developed a nickel-catalysed regio- and stereoselective hydrocyanation of alkynoates that gives syn-β-cyanoalkenes. DFT calculations suggest that a favored transition state promotes Cα–H bond formation for determining regio- and stereoselectivity of the products.

  我们开发了一种镍催化的炔酸酯区域和立体选择性氢氰化反应，可生成顺式-β-氰基烯烃。 DFT 计算表明，有利的过渡态促进 Cα-H 键的形成，从而确定产物的区域选择性和立体选择性。
• Mowry; Rossow, Journal of the American Chemical Society, 1945, vol. 67, p. 927
  作者：Mowry、Rossow

  DOI：——

  日期：——
• Chemoenzymatic Asymmetric Synthesis of Pregabalin Precursors via Asymmetric Bioreduction of β-Cyanoacrylate Esters Using Ene-Reductases
  作者：Christoph K. Winkler、Dorina Clay、Simon Davies、Pat O’Neill、Paul McDaid、Sebastien Debarge、Jeremy Steflik、Mike Karmilowicz、John W. Wong、Kurt Faber

  DOI：10.1021/jo302484p

  日期：2013.2.15

  The asymmetric bioreduction of a library of beta-cyanoacrylate esters using ene-reductases was studied with the aim to provide a biocatalytic route to precursors for GABA analogues, such as pregabalin. The stereochemical outcome could be controlled by substrate-engineering through size-variation of the ester moiety and by employing stereochemically pure (E)- or (Z)-isomers, which allowed to access both enantiomers of each product in up to quantitative conversion in enantiomerically pure form. In addition, stereoselectivities and conversions could be improved by mutant variants of OPR1, and the utility of the system was demonstrated by preparative-scale applications.