ethyl (S)-2-benzyl-2-methylacetoacetate | 89656-86-0

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: ethyl (S)-2-benzyl-2-methylacetoacetate
• 英文别名: ethyl (2S)-2-benzyl-2-methyl-3-oxobutanoate
• CAS: 89656-86-0
• 化学式: C₁₄H₁₈O₃
• 分子量: 234.295
• InChiKey: QIZLWQIYZQZSHX-AWEZNQCLSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.7
• 重原子数：
  17
• 可旋转键数：
  6
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.43
• 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：

  ethyl (S)-2-benzyl-2-methylacetoacetate 在 sodium azide 、 甲烷磺酸 、 氢气 、 methyloxirane 作用下， 以 氯仿 为溶剂， 反应 1.0h， 生成 2-甲基-L-苯丙氨酸一水物
  参考文献：
  名称：

  通过α，α-双烷基化的β-酮酯的Schmidt重排不对称合成α-烷基化的α-氨基酸

  摘要：

  通过光学活性α，α-双烷基化β-酮酯的施密特重排，可以高收率和光学纯度获得α-烷基化的α-氨基酸。

  DOI：

  10.1016/s0040-4039(00)80107-0
• 作为产物：
  描述：

  ethyl (2R)-2-benzyl-2-methyl-3-[(1S,2S)-2-hydroxycyclohexyloxy]-3-butenoate 在 三氟化硼乙醚 作用下， 以 乙醇 、 水 为溶剂， 反应 3.0h， 以73%的产率得到ethyl (S)-2-benzyl-2-methylacetoacetate
  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

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
• 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.
• Catalytic asymmetric alkylation of α-cyanocarboxylates and acetoacetates using a phase-transfer catalyst
  作者：Kazuhiro Nagata、Daisuke Sano、Yu Shimizu、Michiko Miyazaki、Takuya Kanemitsu、Takashi Itoh

  DOI：10.1016/j.tetasy.2009.10.018

  日期：2009.11

  The catalytic asymmetric alkylation of alpha-cyanocarboxylates and acetoacetates with an alkyl halide was performed under phase-transfer conditions to afford compounds which have a chiral quaternary carbon with up to 97% and 94% ee, respectively. As applications of this method, chiral 2-oxindole derivatives and a beta-lactam derivative were synthesized. (C) 2009 Elsevier Ltd. All rights reserved.
• 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：——