(R)-3,3-Dimethyl-2-((R)-1-phenyl-ethylamino)-butyronitrile

• 分子结构分类: 有机化合物 - 有机氮化合物
• 英文名称: (R)-3,3-Dimethyl-2-((R)-1-phenyl-ethylamino)-butyronitrile
• 英文别名: (2R)-3,3-dimethyl-2-[[(1R)-1-phenylethyl]amino]butanenitrile
• 化学式: C₁₄H₂₀N₂
• 分子量: 216.326
• InChiKey: GTKIFEDYSFURFE-YPMHNXCESA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.2
• 重原子数：
  16
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  35.8
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为产物：
  描述：

  氰化钾 、 特戊醛 、 α-苯乙胺 在 sodium hydrogensulfite 作用下， 以 甲醇 、 水 为溶剂， 生成 (R)-3,3-Dimethyl-2-((R)-1-phenyl-ethylamino)-butyronitrile 、 (R,S)-3,3-dimethyl-2-(1-phenylethylamino)butyronitrile
  参考文献：
  名称：

  Thermodynamically controlled 1,3-asymmetric induction in an acyclic system: equilibration of .alpha.-amino nitriles derived from .alpha.-alkylbenzylamines and aldehydes

  摘要：

  Acyclic-alpha-amino nitriles 1, derived from alpha-alkylbenzylamines 3 and aldehydes 4 via a Strecker-type reaction, readily epimerize in MeOH at the newly emerged asymmetric center alpha-to the cyano group. The equilibrium diastereomeric ratio [(R*,R*)-1]:[(R*,S*)-1] varies from 73:27 for le to 90:10 for 1h. The latter ratio is unprecedentedly high for thermodynamically controlled 1,3-asymmetric induction. The aromatic group and a bulky alkyl group (R1) of the parent amine 3 are required to obtain high concentrations of (R*,R*)-1, whereas the bulkiness of the alkyl group (R2) of the parent aldehyde 4 has little effect. The reasons for the thermodynamic predominance of (R*,R*)-1 over (R*,S*)-1 were addressed by MM2 calculations, which predicted the most stable conformers of (R*,R*)-1 and (R*,S*)-1. The structures of these conformers were verified by H-1 NMR spectroscopy and X-ray crystallography.

  DOI：

  10.1021/jo00003a061

文献信息

• Lithium perchlorate/ diethylether catalyzed aminocyanation of aldehydes
  作者：Akbar Heydari、Parinaz Fatemi、Abdol-Ali Alizadeh

  DOI：10.1016/s0040-4039(98)00354-2

  日期：1998.5

  A simple and efficient one-pot method was developed to give α-aminonitriles from aldehydes + amines + TMSCN in LPDE. Optically active α-aminonitriles were snythesized by using (S)-(−)- or (R)-(+) α-methylbenzylamine, (S)-(−) α-methylbenzylamine affords predominantly S-aminonitriles and (R)-(+) α-methylbenzylamine leads to the R-aminonitriles.

  开发了一种简单有效的一锅法，由LPDE中的醛+胺+ TMSCN生成α-氨基腈。通过使用（S）-（-）-或（R）-（+）α-甲基苄胺来合成旋光性α-氨基腈，（S）-（-）α-甲基苄胺主要提供S-氨基腈和（R）-（ +）α-甲基苄胺导致R-氨基腈。
• One-pot synthesis of α-aminonitriles from alkyl and aryl cyanides: a Strecker reaction via aldimine alanes
  作者：Szabolcs Sipos、István Jablonkai

  DOI：10.1016/j.tetlet.2009.02.004

  日期：2009.4

  A one-pot Strecker reaction using various alkyl, arylalkyl and arylnitriles is developed. Aldimine alanes were generated in situ from nitriles by the addition of diisobutylaluminium hydride, and were converted into the corresponding imines on reaction with (S)-(-)-1-phenylethylamine. Nucleophilic addition to the imines in the presence of catalytic triethylamine, using acetone cyanohydrin as a cyanide source, provided alpha-aminonitriles. (C) 2009 Elsevier Ltd. All rights reserved.
• Thermodynamically controlled 1,3-asymmetric induction in an acyclic system: equilibration of .alpha.-amino nitriles derived from .alpha.-alkylbenzylamines and aldehydes
  作者：Takashi Inaba、Makoto Fujita、Katsuyuki Ogura

  DOI：10.1021/jo00003a061

  日期：1991.2

  Acyclic-alpha-amino nitriles 1, derived from alpha-alkylbenzylamines 3 and aldehydes 4 via a Strecker-type reaction, readily epimerize in MeOH at the newly emerged asymmetric center alpha-to the cyano group. The equilibrium diastereomeric ratio [(R*,R*)-1]:[(R*,S*)-1] varies from 73:27 for le to 90:10 for 1h. The latter ratio is unprecedentedly high for thermodynamically controlled 1,3-asymmetric induction. The aromatic group and a bulky alkyl group (R1) of the parent amine 3 are required to obtain high concentrations of (R*,R*)-1, whereas the bulkiness of the alkyl group (R2) of the parent aldehyde 4 has little effect. The reasons for the thermodynamic predominance of (R*,R*)-1 over (R*,S*)-1 were addressed by MM2 calculations, which predicted the most stable conformers of (R*,R*)-1 and (R*,S*)-1. The structures of these conformers were verified by H-1 NMR spectroscopy and X-ray crystallography.