(S)-methyl 3-cyanopentanoate | 881315-65-7

• 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: (S)-methyl 3-cyanopentanoate
• 英文别名: (S)-methyl-3-cyanopentanoate；methyl (3S)-3-cyanopentanoate
• CAS: 881315-65-7
• 化学式: C₇H₁₁NO₂
• 分子量: 141.17
• InChiKey: NGNRQBRSYZDCPO-LURJTMIESA-N

物化性质

• 沸点：
  229.7±23.0 °C(Predicted)
• 密度：
  0.998±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0.7
• 重原子数：
  10
• 可旋转键数：
  4
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.71
• 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：

  (S)-methyl 3-cyanopentanoate 在 镍 氢气 作用下， 以 甲醇 为溶剂， 70.0 ℃ 、2.0 MPa 条件下， 反应 16.0h， 以95%的产率得到(S)-4-Ethylpyrrolidin-2-one
  参考文献：
  名称：

  Asymmetric Synthesis of β-Substituted γ-Lactams Employing the SAMP-/RAMP-Hydrazone Methodology. Application to the Synthesis of (R)-(-)-Baclofen

  摘要：

  A short and efficient asymmetric synthesis of beta-substituted gamma-lactams is described. Key steps are the alpha-alkylation of aldehyde SAMP-hydrazones with alkyl bromoacetates, their MMPP mediated conversion to the corresponding nitriles and a reductive cyclization with Raney Ni or Ni boride to the title pyrrolidin-2-ones. The P-substituted gamma-lactams are obtained in three steps, good overall yields (27-78%) and excellent enantiomeric excesses (ee = 93-99%). The applicability of this procedure for the asymmetric synthesis of GABAs (gamma-aminobutyric acids) is demonstrated for (R)-(-)-baclofen hydrochloride, which is obtained in 4 steps, 55% yield and 94% ee.

  DOI：

  10.3987/com-05-s(k)41
• 作为产物：
  描述：

  (Z)-ethyl 3-(trifluoromethylsulfonyloxy)pent-2-enoate 在 titanium(IV) tetraethanolate 、 四(三苯基膦)钯 、 EBP₁ from Candida albicans 、 乙二醇 、 还原型辅酶Ⅰ 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 157.0h， 生成 (S)-methyl 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

文献信息

• Rationalisation of the stereochemical outcome of ene-reductase-mediated bioreduction of α,β-difunctionalised alkenes
  作者：Elisabetta Brenna、Michele Crotti、Francesco G. Gatti、Alessia Manfredi、Daniela Monti、Fabio Parmeggiani、Andrea Pugliese、Davila Zampieri

  DOI：10.1016/j.molcatb.2013.12.020

  日期：2014.3

  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.