(Z)-3-氰基丁-2-烯酸乙酯 | 40595-04-8

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 脂肪酰基
• 中文名称: (Z)-3-氰基丁-2-烯酸乙酯
• 英文名称: (Z)-ethyl 3-cyanobut-2-enoate
• 英文别名: ethyl (Z)-3-cyanobut-2-enoate
• CAS: 40595-04-8
• 化学式: C₇H₉NO₂
• 分子量: 139.154
• InChiKey: ZRKOIZAQWIGYPW-XQRVVYSFSA-N

物化性质

• 沸点：
  119-120 °C(Press: 24 Torr)
• 密度：
  1.040 g/cm3(Temp: 25 °C)

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

安全信息

• 海关编码：
  2926909090

反应信息

• 作为反应物：
  描述：

  (Z)-3-氰基丁-2-烯酸乙酯 在 palladium 10% on activated carbon 、 氢气 作用下， 以 四氢呋喃 为溶剂， 20.0 ℃ 、101.33 kPa 条件下， 以97%的产率得到3-氰基丁酸乙酯
  参考文献：
  名称：

  Chemoenzymatic Asymmetric Synthesis of Pregabalin Precursors via Asymmetric Bioreduction of β-Cyanoacrylate Esters Using Ene-Reductases

  摘要：

  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.

  DOI：

  10.1021/jo302484p
• 作为产物：
  描述：

  乙酰乙酸乙酯 在 四(三苯基膦)钯 、 四甲基氢氧化铵 作用下， 以 正庚烷 、 水 、 N,N-二甲基甲酰胺 为溶剂， 反应 17.75h， 生成 (Z)-3-氰基丁-2-烯酸乙酯
  参考文献：
  名称：

  Chemoenzymatic Asymmetric Synthesis of Pregabalin Precursors via Asymmetric Bioreduction of β-Cyanoacrylate Esters Using Ene-Reductases

  摘要：

  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.

  DOI：

  10.1021/jo302484p

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.