methyl (S)-1-benzyl-2-oxocyclohexanecarboxylate | 89656-84-8

• 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: methyl (S)-1-benzyl-2-oxocyclohexanecarboxylate
• 英文别名: methyl (R)-1-benzyl-2-oxocyclohexanecarboxylate；methyl (1S)-1-benzyl-2-oxocyclohexane-1-carboxylate
• CAS: 89656-84-8
• 化学式: C₁₅H₁₈O₃
• 分子量: 246.306
• InChiKey: HCMBZQZUCUJZDB-HNNXBMFYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.8
• 重原子数：
  18
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.47
• 拓扑面积：
  43.4
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  重氮甲烷 、 methyl (S)-1-benzyl-2-oxocyclohexanecarboxylate 生成 methyl (S)-1-carbomethoxy-2-oxocyclohexylacetate
  参考文献：
  名称：

  Stereoselective reactions. XXI. Asymmetric alkylation of α-alkyl β-keto esters to α,α-dialkyl β-keto esters having either (R)- or (S)-chiral quaternary center depending on the solvent system

  摘要：

  Asymmetric alkylation reaction of chiral enamines prepared from alpha-alkyl beta-keto esters and (S)-valine tert-butyl ester leading to either enantiomer is described. Lithiated chiral enamines can be alkylated with alkyl halides in a toluene solvent in the presence of HMPA to give, after hydrolysis, alpha,alpha-dialkyl beta-keto esters in 70-99%ee. The reactions in the presence of THF, dioxolane, or trimethylamine. instead of HMPA, afford the corresponding antipodes with enantiomeric purities of 44-92%ee. The present method provides a procedure for the synthesis of both enantiomers of alpha,alpha-dialkyl beta-keto esters in high enantiomeric purities starting from the same chiral enamines.

  DOI：

  10.1016/s0040-4020(01)80346-x
• 作为产物：
  描述：

  methyl (1R)-1-benzyl-2-<(1S,2S)-2-hydroxycyclohexan-1-yl>oxy-1-methyl-2-cyclohexen-1-carboxylate 在 甲醇 、 三氟化硼乙醚 、 水 作用下， 以93%的产率得到methyl (S)-1-benzyl-2-oxocyclohexanecarboxylate
  参考文献：
  名称：

  Asymmetric alkylation using chiral cyclic diols to prepare a quaternary carbon

  摘要：

  Asymmetric alkylation of cyclic and acyclic beta-keto ester acetals (4, 5, 13, 14, and 18) with C-2-symmetric cycloalkane-1,2-dioxy moiety proceeded in a highly diastereoselective manner to afford enol ethers (9-12, 15-17, 19a-c) with a chiral quaternary carbon.

  DOI：

  10.1016/s0040-4020(01)87012-5

文献信息

• Asymmetric alkylation of .alpha.-alkyl .beta.-keto esters
  作者：Kiyoshi Tomioka、Kaori Ando、Yutaka Takemasa、Kenji Koga

  DOI：10.1021/ja00321a050

  日期：1984.5

  Diastereoselective alkylation de lithio enamines obtenues a partir d'α-alkyl β-cetoesters et du (S)-valinate de t-butyle

  非对映选择性烷基化脱硫烯胺减少部分 d'α-烷基 β-cetoesters et du (S)-valinate de t-butyle
• Kato Keisuke, Suemune Hiroshi, Sakai Kiyoshi, Tetrahedron, 50 (1994) N 11, S 3315-3326
  作者：Kato Keisuke, Suemune Hiroshi, Sakai Kiyoshi

  DOI：——

  日期：——
• Stereoselective reactions. XXI. Asymmetric alkylation of α-alkyl β-keto esters to α,α-dialkyl β-keto esters having either (R)- or (S)-chiral quaternary center depending on the solvent system
  作者：Kaori Ando、Yataka Takemasa、Kiyoshi Tomioka、Kenji Koga

  DOI：10.1016/s0040-4020(01)80346-x

  日期：——

  Asymmetric alkylation reaction of chiral enamines prepared from alpha-alkyl beta-keto esters and (S)-valine tert-butyl ester leading to either enantiomer is described. Lithiated chiral enamines can be alkylated with alkyl halides in a toluene solvent in the presence of HMPA to give, after hydrolysis, alpha,alpha-dialkyl beta-keto esters in 70-99%ee. The reactions in the presence of THF, dioxolane, or trimethylamine. instead of HMPA, afford the corresponding antipodes with enantiomeric purities of 44-92%ee. The present method provides a procedure for the synthesis of both enantiomers of alpha,alpha-dialkyl beta-keto esters in high enantiomeric purities starting from the same chiral enamines.
• Asymmetric alkylation using chiral cyclic diols to prepare a quaternary carbon
  作者：Keisuke Kato、Hiroshi Suemune、Kiyoshi Sakai

  DOI：10.1016/s0040-4020(01)87012-5

  日期：1994.3

  Asymmetric alkylation of cyclic and acyclic beta-keto ester acetals (4, 5, 13, 14, and 18) with C-2-symmetric cycloalkane-1,2-dioxy moiety proceeded in a highly diastereoselective manner to afford enol ethers (9-12, 15-17, 19a-c) with a chiral quaternary carbon.