ethyl (2RS)-3,3-<(S,S)-cyclohexane-1,2-dioxy>-2-methylbutanoate | 340039-86-3

• 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 (2RS)-3,3-<(S,S)-cyclohexane-1,2-dioxy>-2-methylbutanoate
• 英文别名: ethyl (2RS)-3,3-[(1S,2S)-cyclohexane-1,2-dioxy]-2-methylbutanoate；ethyl (2RS)-3,3-((S,S)-cyclohexane-1,2-dioxy)-2-methylbutanoate；ethyl 2-[(3aS,7aS)-2-methyl-3a,4,5,6,7,7a-hexahydro-1,3-benzodioxol-2-yl]propanoate
• CAS: 340039-86-3
• 化学式: C₁₃H₂₂O₄
• 分子量: 242.315
• InChiKey: ZWWILLBYQXHOEE-DVRYWGNFSA-N

物化性质

• 沸点：
  302.7±12.0 °C(Predicted)
• 密度：
  1.054±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.1
• 重原子数：
  17
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.92
• 拓扑面积：
  44.8
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  ethyl (2RS)-3,3-<(S,S)-cyclohexane-1,2-dioxy>-2-methylbutanoate 在 六甲基磷酰三胺 、 sodium azide 、 甲烷磺酸 、 三氟化硼乙醚 、 lithium diisopropyl amide 作用下， 以 四氢呋喃 、 乙醇 、 正己烷 、 氯仿 、 水 为溶剂， 反应 14.5h， 生成 (R)-N-acetyl-α-methylphenylalanine ethyl ester
  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
• 作为产物：
  描述：

  2-甲基乙酰乙酸乙酯 、 (1S,2s)-反式-1,2-环己二醇 在 对甲苯磺酸 作用下， 以 苯 为溶剂， 反应 10.0h， 以81%的产率得到ethyl (2RS)-3,3-<(S,S)-cyclohexane-1,2-dioxy>-2-methylbutanoate
  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 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.
• Application of chiral cyclic diols to asymmetric alkylation
  作者：Keisuke Kato、Hiroshi Suemune、Koyoshi Sakai

  DOI：10.1016/0040-4039(92)88062-a

  日期：1992.1

  Chiral cyclic (6- or 7-membered ring) diols were found to be excellent chiral auxiliaries for asymmetric alkylation of cyclic (or acyclic) beta-keto esters.
• 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：——
• Asymmetric Synthesis of α,α-Disubstituted α-Amino Acids Using (<i>S</i>,<i>S</i>)-Cyclohexane-1,2-diol as a Chiral Auxiliary
  作者：Masakazu Tanaka、Makoto Oba、Koichi Tamai、Hiroshi Suemune

  DOI：10.1021/jo001423m

  日期：2001.4.1

  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.