4-hydroxy-3,5-dimethyl-3-phenylsulfanyl-dihydro-furan-2-one | 950765-88-5

• 分子结构分类: 有机化合物 - 有机硫化合物 - 硫醚类
• 英文名称: 4-hydroxy-3,5-dimethyl-3-phenylsulfanyl-dihydro-furan-2-one
• 英文别名: (3R,4R,5S)-4-hydroxy-3,5-dimethyl-3-phenylsulfanyloxolan-2-one
• CAS: 950765-88-5
• 化学式: C₁₂H₁₄O₃S
• 分子量: 238.307
• InChiKey: LMFZSDXSVWTBPR-MKPLZMMCSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.2
• 重原子数：
  16
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.42
• 拓扑面积：
  71.8
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  4-hydroxy-3,5-dimethyl-3-phenylsulfanyl-dihydro-furan-2-one 在 间氯过氧苯甲酸 作用下， 以84%的产率得到(3R,4R,5S)-dihydro-4-hydroxy-3,5-dimethyl-3-(phenylsulfinyl)-furan-2(3H)-one
  参考文献：
  名称：

  Stereoisomerization of β-Hydroxy-α-sulfenyl-γ-butyrolactones Controlled by Two Concomitant 1,4-Type Nonbonded Sulfur−Oxygen Interactions As Analyzed by X-ray Crystallography

  摘要：

  We have synthesized nine beta-hydroxy-alpha-sulfenyl-gamma-butyrolactones having different substituents. The syn-anti or syn-syn lactones (or any mixture of both) invariably isomerized into syn-anti/syn-syn lactones in a ratio of similar to 6/4. The other two possible isomeric lactones (anti-syn or anti-anti) were never observed. The crystal structures of syn-syn lactones have been determined. We found sulfur-oxygen distances to be less than the sum of the van der Waals radii (3.3 angstrom), with the angle formed among the hydroxylic oxygen, sulfur, and quaternary aromatic carbon being close to 180 degrees. In addition, carbonylic oxygen-sulfur is directed <40 degrees from the perpendicular to the C-S-C. Theoretical calculations were performed which emphasize the directionality of the sulfur-oxygen interaction. The X-ray and theoretical studies demonstrate that two concomitant, attractive 1,4 intramolecular interactions of divalent sulfur with both carbonyl and hydroxyl oxygens are the driving force for the aforementioned stereochemical preference. Then nonbonded sulfur-oxygen interactions would control the stereoselectivity of the reaction. The same features are observed in the X-ray structure of a beta-hydroxy-alpha-sulfinyl-gamma-butyrolactone.

  DOI：

  10.1021/jo1009454
• 作为产物：
  描述：

  (4S,2E)-ethyl 4-hydroxy-2-methylpent-2-enoate 在 六甲基磷酰三胺 、 二叔丁基过氧化物 、 乙基锂 、 sodium hydride 作用下， 以 四氢呋喃 、 环己烷 、 苯 为溶剂， 反应 169.33h， 生成 4-hydroxy-3,5-dimethyl-3-phenylsulfanyl-dihydro-furan-2-one
  参考文献：
  名称：

  Highly Stereoselective Epoxidation of α-Methyl-γ-hydroxy-α,β-unsaturated Esters:  Rationalization and Synthetic Applications

  摘要：

  The diastereoselectivity of the nucleophilic epoxidation of gamma-hydroxy-alpha, beta-unsaturated esters having a methyl substituent at the alpha- or beta-position was investigated. Epoxidation of the alpha-methyl-substituted enoate was highly stereoselective, giving rise to the syn isomer. This finding was used to perform an enantioselective synthesis of a natural product having a beta-hydroxy-alpha-methylene-gamma-butyrolactone motif. The nucleophilic epoxidation of enoates was found to be irreversible. Models to explain the observed stereoselectivities are proposed.

  DOI：

  10.1021/jo0709955

文献信息

• Highly Stereoselective Epoxidation of α-Methyl-γ-hydroxy-α,β-unsaturated Esters:  Rationalization and Synthetic Applications
  作者：Irakusne López、Santiago Rodríguez、Javier Izquierdo、Florenci V. González

  DOI：10.1021/jo0709955

  日期：2007.8.1

  The diastereoselectivity of the nucleophilic epoxidation of gamma-hydroxy-alpha, beta-unsaturated esters having a methyl substituent at the alpha- or beta-position was investigated. Epoxidation of the alpha-methyl-substituted enoate was highly stereoselective, giving rise to the syn isomer. This finding was used to perform an enantioselective synthesis of a natural product having a beta-hydroxy-alpha-methylene-gamma-butyrolactone motif. The nucleophilic epoxidation of enoates was found to be irreversible. Models to explain the observed stereoselectivities are proposed.
• Stereoisomerization of β-Hydroxy-α-sulfenyl-γ-butyrolactones Controlled by Two Concomitant 1,4-Type Nonbonded Sulfur−Oxygen Interactions As Analyzed by X-ray Crystallography
  作者：Florenci V. González、Amit Jain、Santiago Rodríguez、José A. Sáez、Cristian Vicent、Gabriel Peris

  DOI：10.1021/jo1009454

  日期：2010.9.3

  We have synthesized nine beta-hydroxy-alpha-sulfenyl-gamma-butyrolactones having different substituents. The syn-anti or syn-syn lactones (or any mixture of both) invariably isomerized into syn-anti/syn-syn lactones in a ratio of similar to 6/4. The other two possible isomeric lactones (anti-syn or anti-anti) were never observed. The crystal structures of syn-syn lactones have been determined. We found sulfur-oxygen distances to be less than the sum of the van der Waals radii (3.3 angstrom), with the angle formed among the hydroxylic oxygen, sulfur, and quaternary aromatic carbon being close to 180 degrees. In addition, carbonylic oxygen-sulfur is directed <40 degrees from the perpendicular to the C-S-C. Theoretical calculations were performed which emphasize the directionality of the sulfur-oxygen interaction. The X-ray and theoretical studies demonstrate that two concomitant, attractive 1,4 intramolecular interactions of divalent sulfur with both carbonyl and hydroxyl oxygens are the driving force for the aforementioned stereochemical preference. Then nonbonded sulfur-oxygen interactions would control the stereoselectivity of the reaction. The same features are observed in the X-ray structure of a beta-hydroxy-alpha-sulfinyl-gamma-butyrolactone.