ethyl (2R)-2-ethyl-3-[(1R,2R)-2-hydroxycyclohexyloxy]-2-(1-methylpropyl)but-3-enoate | 339991-86-5

• 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: ethyl (2R)-2-ethyl-3-[(1R,2R)-2-hydroxycyclohexyloxy]-2-(1-methylpropyl)but-3-enoate
• 英文别名: ethyl (2R)-2-ethyl-2-isobutyl-3-[(1R,2R)-2-hydroxycyclohexyloxy]-3-butenoate；ethyl (2R)-2-ethyl-2-[1-[(1R,2R)-2-hydroxycyclohexyl]oxyethenyl]-4-methylpentanoate
• CAS: 339991-86-5
• 化学式: C₁₈H₃₂O₄
• 分子量: 312.45
• InChiKey: DNFNNBQPYVBUMX-JFIYKMOQSA-N

物化性质

• 沸点：
  427.6±45.0 °C(Predicted)
• 密度：
  1.00±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.1
• 重原子数：
  22
• 可旋转键数：
  9
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.83
• 拓扑面积：
  55.8
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  ethyl (2R)-2-ethyl-3-[(1R,2R)-2-hydroxycyclohexyloxy]-2-(1-methylpropyl)but-3-enoate 在 sodium azide 、 甲烷磺酸 、 三氟化硼乙醚 作用下， 以 乙醇 、 氯仿 、 水 为溶剂， 反应 25.0h， 生成 ethyl (S)-N-acetyl-α-ethylleucinate
  参考文献：
  名称：

  Conformation of Peptides Containing a Chiral -Ethylated ,-Disubstituted -Amino Acid: (S)--Ethylleucine (=(2S)-2-Amino-2-ethyl-4-methylpentanoic Acid) within Sequences of Dimethylglycine and Diethylglycine Residues

  摘要：

  An optically active (S)-alpha-ethylleucine ((S)-alphaEtLeu) as a chiral alpha-ethylated alpha,alpha-disubstituted alpha-amino acid was synthesized by means of a chiral acetal auxiliary of (R,R)-cyclohexane-1,2-diol. The chiral alpha-ethylated alpha,alpha-disubstituted amino acid (S)-alphaEtLeu was introduced into the peptides constructed from 2aminoisobutyric acid (= dimethylglycine, Aib), and also into the peptide prepared from diethylglycine (Deg). The X-ray crystallographic analysis revealed that both right-handed (P) and left-handed (M) 3(10)-helical structures exist in the solid state of CF3CO-(Aib)(2)-[(S)-alphaEtLeu]-(Aib)(2)-OEt (14) and CF3CO-[(S)-alphaEtLeu]-(Deg)(4)-OEt (18), respectively. The IR, CD, and H-1-NMR spectra indicated that the dominant conformation of pentapeptides 14 and CF3CO-[(S)-alphaEtLeu]-(Aib)(4)-OEt (16) in solution is a 3(10)-helical structure, and that of 18 in solution is a planar C-5 conformation. The conformation of peptides was also studied by molecular-mechanics calculations.

  DOI：

  10.1002/1522-2675(200210)85:10<3197::aid-hlca3197>3.0.co;2-y
• 作为产物：
  描述：

  2-乙基乙酰乙酸乙酯 在 六甲基磷酰三胺 、 对甲苯磺酸 、 lithium diisopropyl amide 作用下， 以 四氢呋喃 、 正己烷 、 苯 为溶剂， 反应 15.5h， 生成 ethyl (2R)-2-ethyl-3-[(1R,2R)-2-hydroxycyclohexyloxy]-2-(1-methylpropyl)but-3-enoate
  参考文献：
  名称：

  Asymmetric Synthesis of α,α-Disubstituted α-Amino Acids Using (S,S)-Cyclohexane-1,2-diol as a Chiral Auxiliary

  摘要：

  Diastereoselective alkylation of ethyl 2-methyl- and/or 2-ethylacetoacetates using the (S,S)cyclohexane-1,2-diol as an acetal chiral auxiliary afforded enol ethers (2a-f and 5a-f) of 92 - > 95% de in 31-70% yields. Removal of the cyclohexane-l,2-diol with BF3-OEt2 afforded beta -keto esters (3 and 6) bearing a chiral quaternary carbon. The beta -keto esters could be easily converted into optically active alpha -methylated and/or alpha -ethylated alpha,alpha -disubstituted amino acids (12 and 13) in 21-99% yields using Schmidt rearrangement.

  DOI：

  10.1021/jo001423m