2-<2'-(methylthio)acetyl>hexahydro-4,4,7-trimethyl-4H-1,3-benzoxathiin | 142798-62-7

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 氧硫烷类
• 英文名称: 2-<2'-(methylthio)acetyl>hexahydro-4,4,7-trimethyl-4H-1,3-benzoxathiin
• 英文别名: 1-[(2R,4aR,7R,8aR)-4,4,7-trimethyl-4a,5,6,7,8,8a-hexahydrobenzo[e][1,3]oxathiin-2-yl]-2-methylsulfanylethanone
• CAS: 142798-62-7
• 化学式: C₁₄H₂₄O₂S₂
• 分子量: 288.475
• InChiKey: AUZYSAXNDFJMPJ-FPQZTECRSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.8
• 重原子数：
  18
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.93
• 拓扑面积：
  76.9
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  phenylmagnesium bromide 、 2-<2'-(methylthio)acetyl>hexahydro-4,4,7-trimethyl-4H-1,3-benzoxathiin 以 四氢呋喃 、 乙醚 为溶剂， 反应 4.0h， 生成 2-<(1'R)-1'-hydroxy-2'-(methylthio)-1'-phenylethyl>hexahydro-4,4,7-trimethyl-4H-1,3-benzoxathiin 、 2-<(1'S)-1'-hydroxy-2'-(methylthio)-1'-phenylethyl>hexahydro-4,4,7-trimethyl-4H-1,3-benzoxathiin
  参考文献：
  名称：

  Addition of organometallic reagents to acyloxathianes. Diastereoselectivity and mechanistic consideration

  摘要：

  The addition of methyl- and phenylmagnesium bromide and phenyllithium to 2-(methoxyacetyl)-, 2-[(tri-isopropylsiloxy)acetyl]-, and 2-[(methylthio)acetyl]hexahydro-4,4,7-trimethyl-4H-1,3-benxozathiin and the corresponding 2'-methyl, 2-(triisopropylsiloxy)propionyl, and 2-(methylthio)butyryl homologs has been Depending on the 2'-substituent, the reagent and (in case of the higher homologs) the configuration at C(2'), these reactions may or may not be highly diastereoselective and may or may not yield the product of Cram's chelate rule involving the oxygen moiety of the oxathiane ring. Explanations for the different stereochemical outcome of the various reactions are suggested.

  DOI：

  10.1021/jo00045a032
• 作为产物：
  描述：

  (甲硫基)乙酸乙酯 、 (4aR,7R,8aR)-4,4,7-Trimethyl-hexahydro-1-oxa-3-thia-naphthalene 在 正丁基锂 作用下， 生成 2-<2'-(methylthio)acetyl>hexahydro-4,4,7-trimethyl-4H-1,3-benzoxathiin 、 2-<2'-(methylthio)acetyl>hexahydro-4,4,7-trimethyl-4H-1,3-benzoxathiin
  参考文献：
  名称：

  Convenient synthesis of .alpha.-heterosubstituted acyloxathianes

  摘要：

  In contrast to simple esters, alpha-alkoxy, alpha-alkylthio, and alpha-dimethylamino esters react with lithiooxathiane 1-Li in good yield to give the corresponding alpha-functionalized 2-acetylhexahydro-4,4,7-trimethyl-4H-1,3-benzoxathiin 2. In some cases, mixtures of diastereomers (2, 2') are obtained. The reaction has been extended to alpha-methoxy- and alpha-[(triisopropylsilyl)oxy]propanoyl and alpha-(methylthio)butanoyl homologs which have chiral centers at C(alpha).

  DOI：

  10.1021/jo00045a031