Methyl 4-<(phenylthio)acetoxy>but-2(E)-enoate | 168258-01-3

• 分子结构分类: 有机化合物 - 有机硫化合物 - 硫醚类
• 英文名称: Methyl 4-<(phenylthio)acetoxy>but-2(E)-enoate
• 英文别名: methyl (E)-4-(2-phenylsulfanylacetyl)oxybut-2-enoate
• CAS: 168258-01-3
• 化学式: C₁₃H₁₄O₄S
• 分子量: 266.318
• InChiKey: UCTXFDRLTSIDMT-VMPITWQZSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.5
• 重原子数：
  18
• 可旋转键数：
  8
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.23
• 拓扑面积：
  77.9
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  Methyl 4-<(phenylthio)acetoxy>but-2(E)-enoate 在 sodium hydride 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 2.0h， 以70%的产率得到Methyl (3R,4S)/(3S,4R)-<5-oxo-4-(phenylthio)tetrahydrofuran-3-yl>acetate
  参考文献：
  名称：

  Stereoselective Synthesis of Highly Substituted .gamma.-Lactones by Diastereoselective Alkylation of .alpha.-(Benzenesulfonyl) Derivatives with Unusual Facial Selectivity

  摘要：

  The oxidation of alpha-(phenylthio) gamma-lactones obtained by the base-induced cyclization of enantiomerically enriched gamma-[(phenylthio) acyl]-alpha,beta-unsaturated esters to sulfones in those cases where the a-carbon has an available proton and further basic alkylation led to an unexpected facial selectivity. The reaction proceeded smoothly with alkylating agents and unsaturated carbonyl compounds, but was unsuccessful when an addition to carbonyl derivatives was attempted. The alkylation reaction was performed over a wide range of substituted substrates in order to investigate the scope and limitations of the method and to have information about the possible origin of the selectivity. The application of the alkylation reaction was extended to the synthesis of bicyclic systems, including a cyclobutane with total stereochemical control. The presence of the alpha-(benzenesulfonyl) group is shown to be essential to achieve the facial selection. In order to rationalize the stereochemical results, extensive semiempirical calculations were performed. The use of MNDO and AM1 permits rationalization of the fact that the alpha-(benzenesulfonyl) group encumbers a diastereoface of the enolate generated in the ring, leading to the observed stereochemistry.

  DOI：

  10.1021/jo00105a027
• 作为产物：
  描述：

  苯硫基乙酸 在 lead(IV) acetate 、 盐酸 、 4-二甲氨基吡啶 、 N,N'-二环己基碳二亚胺 作用下， 以 四氢呋喃 、 二氯甲烷 、 苯 为溶剂， 反应 6.25h， 生成 Methyl 4-<(phenylthio)acetoxy>but-2(E)-enoate
  参考文献：
  名称：

  Stereoselective Synthesis of Highly Substituted .gamma.-Lactones by Diastereoselective Alkylation of .alpha.-(Benzenesulfonyl) Derivatives with Unusual Facial Selectivity

  摘要：

  The oxidation of alpha-(phenylthio) gamma-lactones obtained by the base-induced cyclization of enantiomerically enriched gamma-[(phenylthio) acyl]-alpha,beta-unsaturated esters to sulfones in those cases where the a-carbon has an available proton and further basic alkylation led to an unexpected facial selectivity. The reaction proceeded smoothly with alkylating agents and unsaturated carbonyl compounds, but was unsuccessful when an addition to carbonyl derivatives was attempted. The alkylation reaction was performed over a wide range of substituted substrates in order to investigate the scope and limitations of the method and to have information about the possible origin of the selectivity. The application of the alkylation reaction was extended to the synthesis of bicyclic systems, including a cyclobutane with total stereochemical control. The presence of the alpha-(benzenesulfonyl) group is shown to be essential to achieve the facial selection. In order to rationalize the stereochemical results, extensive semiempirical calculations were performed. The use of MNDO and AM1 permits rationalization of the fact that the alpha-(benzenesulfonyl) group encumbers a diastereoface of the enolate generated in the ring, leading to the observed stereochemistry.

  DOI：

  10.1021/jo00105a027

文献信息

• Stereoselective Synthesis of Highly Substituted .gamma.-Lactones by Diastereoselective Alkylation of .alpha.-(Benzenesulfonyl) Derivatives with Unusual Facial Selectivity
  作者：Carmen M. Rodriquez、Tomas Martin、Miguel A. Ramirez、Victor S. Martin

  DOI：10.1021/jo00105a027

  日期：1994.12

  The oxidation of alpha-(phenylthio) gamma-lactones obtained by the base-induced cyclization of enantiomerically enriched gamma-[(phenylthio) acyl]-alpha,beta-unsaturated esters to sulfones in those cases where the a-carbon has an available proton and further basic alkylation led to an unexpected facial selectivity. The reaction proceeded smoothly with alkylating agents and unsaturated carbonyl compounds, but was unsuccessful when an addition to carbonyl derivatives was attempted. The alkylation reaction was performed over a wide range of substituted substrates in order to investigate the scope and limitations of the method and to have information about the possible origin of the selectivity. The application of the alkylation reaction was extended to the synthesis of bicyclic systems, including a cyclobutane with total stereochemical control. The presence of the alpha-(benzenesulfonyl) group is shown to be essential to achieve the facial selection. In order to rationalize the stereochemical results, extensive semiempirical calculations were performed. The use of MNDO and AM1 permits rationalization of the fact that the alpha-(benzenesulfonyl) group encumbers a diastereoface of the enolate generated in the ring, leading to the observed stereochemistry.