(2RS,4RS,6RS)-6-methyl-2,4,6-tris(trifluoromethyl)tetrahydro-2H-pyran-2,4-diol

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 氧烷类
• 英文名称: (2RS,4RS,6RS)-6-methyl-2,4,6-tris(trifluoromethyl)tetrahydro-2H-pyran-2,4-diol
• 英文别名: 6-methyl-2,4,6-tris(trifluoromethyl)tetrahydro-2H-pyran-2,4-diol；(2S,4S,6S)-6-methyl-2,4,6-tris(trifluoromethyl)oxane-2,4-diol
• 化学式: C₉H₉F₉O₃
• 分子量: 336.154
• InChiKey: ZHZPKMZKYBQGKG-ZLUOBGJFSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.7
• 重原子数：
  21
• 可旋转键数：
  0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  49.7
• 氢给体数：
  2
• 氢受体数：
  12

反应信息

• 作为反应物：
  描述：

  (2RS,4RS,6RS)-6-methyl-2,4,6-tris(trifluoromethyl)tetrahydro-2H-pyran-2,4-diol 以 氘代甲醇 为溶剂， 生成 (2SR,4RS,6RS)-6-methyl-2,4,6-tris(trifluoromethyl)tetrahydro-2H-pyran-2,4-diol
  参考文献：
  名称：

  Trimerization Products of Trifluoroacetone:  Critical Solvent Effect on Position and Kinetics of Anomeric Equilibria

  摘要：

  In the presence of bases, trifluoroacetone is known to trimerize leading to configurationally labile 6-methyl-2,4,6-tris(trifluoromethyl)tetrahydro 2H-pyran-2,4-diols 1a,b and 2a,b, structurally close to fluorinated carbohydrates. We report herein a complete study of their behavior in solution. The remarkable solvent effect on the two equilibria (1a double left right arrow 1b; 2a double left right arrow 2b) was rationalized using solvent basicity measures and polarity scales. Solvents of weak donor number were found to favor the diastereoisomers 1a and 2a, which were subsequently isolated. According to their X-ray analyses, they both possess a concave structure with 1,3-cis-diaxial hydroxyl groups. A complementary kinetic study illustrated that acidic conditions can drastically reduce the equilibration rate, allowing the use of a wide range of solvents. Finally, a reexamination of previously published trimerization conditions using sodium or magnesium amalgam revealed that, contrary to the suggestion by two independent reports, 1,3,5-tris(trifluoromethyl)cyclohexane-1,3,5-triol 3/4 was neither formed as the principal product in place of 1a,b and 2a,b nor could it be detected as a minor product.

  DOI：

  10.1021/jo701669p
• 作为产物：
  描述：

  (2SR,4RS,6RS)-6-methyl-2,4,6-tris(trifluoromethyl)tetrahydro-2H-pyran-2,4-diol 以 氘代甲醇 为溶剂， 生成 (2RS,4RS,6RS)-6-methyl-2,4,6-tris(trifluoromethyl)tetrahydro-2H-pyran-2,4-diol
  参考文献：
  名称：

  Trimerization Products of Trifluoroacetone:  Critical Solvent Effect on Position and Kinetics of Anomeric Equilibria

  摘要：

  In the presence of bases, trifluoroacetone is known to trimerize leading to configurationally labile 6-methyl-2,4,6-tris(trifluoromethyl)tetrahydro 2H-pyran-2,4-diols 1a,b and 2a,b, structurally close to fluorinated carbohydrates. We report herein a complete study of their behavior in solution. The remarkable solvent effect on the two equilibria (1a double left right arrow 1b; 2a double left right arrow 2b) was rationalized using solvent basicity measures and polarity scales. Solvents of weak donor number were found to favor the diastereoisomers 1a and 2a, which were subsequently isolated. According to their X-ray analyses, they both possess a concave structure with 1,3-cis-diaxial hydroxyl groups. A complementary kinetic study illustrated that acidic conditions can drastically reduce the equilibration rate, allowing the use of a wide range of solvents. Finally, a reexamination of previously published trimerization conditions using sodium or magnesium amalgam revealed that, contrary to the suggestion by two independent reports, 1,3,5-tris(trifluoromethyl)cyclohexane-1,3,5-triol 3/4 was neither formed as the principal product in place of 1a,b and 2a,b nor could it be detected as a minor product.

  DOI：

  10.1021/jo701669p

文献信息

• Base-catalyzed diastereoselective trimerization of trifluoroacetone
  作者：Anthony P. Silvestri、Philip E. Dawson

  DOI：10.1039/c7ob01094j

  日期：——

  adhesion to both inorganic and biological substrates. Incorporation of these moieties into valuable constructs typically require complex synthetic routes that have limited their use. Here, the base-catalyzed diastereoselective synthesis of 6-methyl- 2,4,6-tris(trifluoromethyl)tetrahydro-2H-pyran-2,4-diol is reported. Trimerization of trifluoroacetone in the presence of 5 mol% KHMDS delivers one of

  两亲性碳氟化合物具有独特的特性，可促进其自组装以及对无机和生物基材的粘附。将这些部分掺入有价值的构建体中通常需要复杂的合成途径，这限制了它们的使用。在此，报道了6-甲基-2,4,6-三（三氟甲基）四氢-2H-吡喃-2,4-二醇的碱催化非对映选择性合成。在没有摩尔色谱的情况下，在5 mol％KHMDS存在下三氟丙酮的三聚反应选择性地以81％的产率提供了四种非对映异构体之一。温度筛选显示了这种三聚反应的可逆性，以及将物料漏斗化为热力学最稳定的恶烷。据报道随后用硼酸官能化。