(S)-(+)-2-<(Dimethylphenylsilyl)oxy>-2-methyl-γ-butyrolactone

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 内酯类
• 英文名称: (S)-(+)-2-<(Dimethylphenylsilyl)oxy>-2-methyl-γ-butyrolactone
• 英文别名: (3S)-3-[dimethyl(phenyl)silyl]oxy-3-methyloxolan-2-one
• 化学式: C₁₃H₁₈O₃Si
• 分子量: 250.37
• InChiKey: WNGNXIXGWDCZBA-ZDUSSCGKSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.82
• 重原子数：
  17
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.46
• 拓扑面积：
  35.5
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为产物：
  描述：

  苯基二甲基氯硅烷 、 α-甲基-γ-丁内酯 在 (+)-<(8,8-dimethoxycamphoryl)sulfonyl>oxaziridine 、 sodium hexamethyldisilazane 作用下， 生成 (S)-(+)-2-<(Dimethylphenylsilyl)oxy>-2-methyl-γ-butyrolactone 、 (R)-(-)-2-<(Dimethylphenylsilyl)oxy>-2-methyl-γ-butyrolactone
  参考文献：
  名称：

  Enantioselective Synthesis of 2-Methyl-2-hydroxy-.gamma.-butyrolactone and Its Application in the Asymmetric Synthesis of Frontalin and Mevalonolactone

  摘要：

  The asymmetric hydroxylation of the enolates of fully substituted acyclic ester 8 and lactone 10 with (camphorylsulfonyl)oxaziridines 1a-c was studied. The stereoselectivities of the tertiary alpha-hydroxy carbonyl products were highly dependent on the enolate structure, the oxidizing reagents, and the reaction conditions. While high diastereoselectivity (up to 94%) was obtained for enolates of fully substituted menthol ester 8 with substoichiometric amounts of oxaziridine 1a, the yields were unsatisfactory. On the other hand, the enantioselective alpha-hydroxylation of the sodium enolate of 2-methyl-gamma-butyrolactone (10) with [(8,8-dimethoxycamphoryl)sulfonyl]oxaziridine (1c) afforded alpha-hydroxy lactone 11a in 70% yield and 84% ee. The enantiomeric excess was improved to > 93% ee by crystallization of the corresponding benzoyl ester 11c. The utility of both enantiomers of 11c were demonstrated in the formal asymmetric syntheses of the pheromone, (1S,5R)-(-)-frontalin (13) and in the asymmetric synthesis of (R)-(-)-mevalonolactone (20).

  DOI：

  10.1021/jo00124a030

文献信息

• Enantioselective Synthesis of 2-Methyl-2-hydroxy-.gamma.-butyrolactone and Its Application in the Asymmetric Synthesis of Frontalin and Mevalonolactone
  作者：Franklin A. Davis、G. Venkat Reddy、Bang-Chi Chen、Anil Kumar、M. Serajul Haque

  DOI：10.1021/jo00124a030

  日期：1995.9

  The asymmetric hydroxylation of the enolates of fully substituted acyclic ester 8 and lactone 10 with (camphorylsulfonyl)oxaziridines 1a-c was studied. The stereoselectivities of the tertiary alpha-hydroxy carbonyl products were highly dependent on the enolate structure, the oxidizing reagents, and the reaction conditions. While high diastereoselectivity (up to 94%) was obtained for enolates of fully substituted menthol ester 8 with substoichiometric amounts of oxaziridine 1a, the yields were unsatisfactory. On the other hand, the enantioselective alpha-hydroxylation of the sodium enolate of 2-methyl-gamma-butyrolactone (10) with [(8,8-dimethoxycamphoryl)sulfonyl]oxaziridine (1c) afforded alpha-hydroxy lactone 11a in 70% yield and 84% ee. The enantiomeric excess was improved to > 93% ee by crystallization of the corresponding benzoyl ester 11c. The utility of both enantiomers of 11c were demonstrated in the formal asymmetric syntheses of the pheromone, (1S,5R)-(-)-frontalin (13) and in the asymmetric synthesis of (R)-(-)-mevalonolactone (20).