methyl (2R)-2-hydroxy-2-[(2S,3S,4R)-4-methyl-2-octyl-5-oxo-4-phenylsulfanyloxolan-3-yl]acetate | 183626-22-4

• 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 (2R)-2-hydroxy-2-[(2S,3S,4R)-4-methyl-2-octyl-5-oxo-4-phenylsulfanyloxolan-3-yl]acetate
• CAS: 183626-22-4
• 化学式: C₂₂H₃₂O₅S
• 分子量: 408.559
• InChiKey: FABAZHWYFODRAU-JZJXAQOMSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.9
• 重原子数：
  28
• 可旋转键数：
  12
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.64
• 拓扑面积：
  98.1
• 氢给体数：
  1
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  methyl (2R)-2-hydroxy-2-[(2S,3S,4R)-4-methyl-2-octyl-5-oxo-4-phenylsulfanyloxolan-3-yl]acetate 在 camphor-10-sulfonic acid 、 间氯过氧苯甲酸 作用下， 以 二氯甲烷 、 甲苯 为溶剂， 反应 74.0h， 生成 (3aR,4S,6aR)-3-亚甲基-4-辛基-4,6a-二氢-3aH-呋喃并[4,3-d]呋喃-2,6-二酮
  参考文献：
  名称：

  A New Stereoselective Synthesis of (−)-Isoavenaciolide and (−)-Avenaciolide

  摘要：

  The synthesis of isoavenaciolide and avenaciolide in their natural enantiomeric forms are described. In both syntheses, alpha-(phenylthio)-beta-[(methoxycarbonyl)methyl]-gamma-lactones obtained by the base-induced cyclization of enantiomerically enriched gamma-[(phenylthio)acyl] alpha,beta-unsaturated esters were used as starting materials. In the isoavenaciolide synthesis the key step is the stereoselective hydroxylation of the enolate generated in the (methoxycarbonyl)methyl chain that permits the bis-lactonization by a double transesterification. The configuration in the quaternary center vicinal to the carbonyl group in the ring was critical in order to obtain successfully the alpha-methylene lactone. In avenaciolide, the stereoselective synthesis of the bis-lactone unit was performed taking advantage of the presence of the phenyl sulfide group which by previous activation was used as leaving group to obtain the fused ring by an intramolecular substitution utilizing the carboxylate of the beta-substituent as nucleophile. In this case, the alpha-methylene lactone was obtained by previously reported methodology.

  DOI：

  10.1021/jo9611935
• 作为产物：
  描述：

  methyl 2-[(2S,3S,4R)-2-octyl-5-oxo-4-phenylsulfanyloxolan-3-yl]acetate 在 正丁基锂 、 MoO5*pyridine*HMPA 、 六甲基二硅氮烷 作用下， 以 四氢呋喃 、 六甲基磷酰三胺 、 正己烷 为溶剂， 反应 7.0h， 生成 methyl (2R)-2-hydroxy-2-[(2S,3S,4R)-4-methyl-2-octyl-5-oxo-4-phenylsulfanyloxolan-3-yl]acetate
  参考文献：
  名称：

  A New Stereoselective Synthesis of (−)-Isoavenaciolide and (−)-Avenaciolide

  摘要：

  The synthesis of isoavenaciolide and avenaciolide in their natural enantiomeric forms are described. In both syntheses, alpha-(phenylthio)-beta-[(methoxycarbonyl)methyl]-gamma-lactones obtained by the base-induced cyclization of enantiomerically enriched gamma-[(phenylthio)acyl] alpha,beta-unsaturated esters were used as starting materials. In the isoavenaciolide synthesis the key step is the stereoselective hydroxylation of the enolate generated in the (methoxycarbonyl)methyl chain that permits the bis-lactonization by a double transesterification. The configuration in the quaternary center vicinal to the carbonyl group in the ring was critical in order to obtain successfully the alpha-methylene lactone. In avenaciolide, the stereoselective synthesis of the bis-lactone unit was performed taking advantage of the presence of the phenyl sulfide group which by previous activation was used as leaving group to obtain the fused ring by an intramolecular substitution utilizing the carboxylate of the beta-substituent as nucleophile. In this case, the alpha-methylene lactone was obtained by previously reported methodology.

  DOI：

  10.1021/jo9611935

文献信息

• A New Stereoselective Synthesis of (−)-Isoavenaciolide and (−)-Avenaciolide
  作者：Carmen M. Rodríguez、Tomás Martín、Victor S. Martín

  DOI：10.1021/jo9611935

  日期：1996.1.1

  The synthesis of isoavenaciolide and avenaciolide in their natural enantiomeric forms are described. In both syntheses, alpha-(phenylthio)-beta-[(methoxycarbonyl)methyl]-gamma-lactones obtained by the base-induced cyclization of enantiomerically enriched gamma-[(phenylthio)acyl] alpha,beta-unsaturated esters were used as starting materials. In the isoavenaciolide synthesis the key step is the stereoselective hydroxylation of the enolate generated in the (methoxycarbonyl)methyl chain that permits the bis-lactonization by a double transesterification. The configuration in the quaternary center vicinal to the carbonyl group in the ring was critical in order to obtain successfully the alpha-methylene lactone. In avenaciolide, the stereoselective synthesis of the bis-lactone unit was performed taking advantage of the presence of the phenyl sulfide group which by previous activation was used as leaving group to obtain the fused ring by an intramolecular substitution utilizing the carboxylate of the beta-substituent as nucleophile. In this case, the alpha-methylene lactone was obtained by previously reported methodology.