(Z)-ethyl 3-cyanopent-2-enoate | 1421868-93-0

• 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: (Z)-ethyl 3-cyanopent-2-enoate
• 英文别名: ethyl 3-cyanopent-2-enoate；ethyl (Z)-3-cyanopent-2-enoate
• CAS: 1421868-93-0
• 化学式: C₈H₁₁NO₂
• 分子量: 153.181
• InChiKey: GWQCCRIUHAGYBK-ALCCZGGFSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.2
• 重原子数：
  11
• 可旋转键数：
  4
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.5
• 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：

  (Z)-ethyl 3-cyanopent-2-enoate 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rac-ethyl 3-cyanopentanoate
  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：

  丙酰乙酸乙酯 在 四(三苯基膦)钯 、 lithium trifluoromethanesulfonate 、 N,N-二异丙基乙胺 作用下， 以 二氯甲烷 、 N,N-二甲基甲酰胺 为溶剂， 反应 17.0h， 生成 (Z)-ethyl 3-cyanopent-2-enoate
  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

• 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。
• 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.