(±)-methyl 2-((2S,5S,6R)-6-(2-(benzyloxy)ethyl)-5-methyltetrahydro-2H-pyran-2-yl)-2-bromopropanoate

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: (±)-methyl 2-((2S,5S,6R)-6-(2-(benzyloxy)ethyl)-5-methyltetrahydro-2H-pyran-2-yl)-2-bromopropanoate
• 英文别名: methyl 2-bromo-2-[(2S,5S,6R)-5-methyl-6-(2-phenylmethoxyethyl)oxan-2-yl]propanoate
• 化学式: C₁₉H₂₇BrO₄
• 分子量: 399.325
• InChiKey: BEAGUCPHMBSJRM-PAGKTPFZSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.1
• 重原子数：
  24
• 可旋转键数：
  8
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.63
• 拓扑面积：
  44.8
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  (±)-methyl 2-((2S,5S,6R)-6-(2-(benzyloxy)ethyl)-5-methyltetrahydro-2H-pyran-2-yl)-2-bromopropanoate 在 三乙基硼 、 三苯基氢化锡 作用下， 以 二氯甲烷 、 甲苯 为溶剂， 以87.5%的产率得到
  参考文献：
  名称：

  A Study of Exocyclic Radical Reductions of Polysubstituted Tetrahydropyrans

  摘要：

  Exocyclic radical reductions were thoroughly investigated in the context of the synthesis of polysubstituted tetrahydropyrans, Which are found in numerous macrolides. The radical precursors studied herein were generated by tandem cycloetherification and iodoetherification reactions or, alternatively, by semicyclic acetals substitutions. DFT calculations (BHandHLYP/TZVP) performed at the transition-state level for the hydrogen radical delivery are in good accordance with the experimental data and enabled the identification of important conformational factors that govern the selectivities obtained. This study demonstrates:that both the preferred reactive conformation of the radical and steric interactions with the incoming hydride have to be considered in order to fully rationalize the levels of diastereoselection generated in acyclic free-radical processes.

  DOI：

  10.1021/jo400721e
• 作为产物：
  描述：

  [5-methyl-6-(2-phenylmethoxyethyl)oxan-2-yl] acetate 、 methyl ((2-bromo-1-methoxyprop-1-en-1-yl)oxy)trimethylsilane 在 四氯化锡 作用下， 以 二氯甲烷 为溶剂， 反应 1.5h， 以83%的产率得到(±)-methyl 2-((2S,5S,6R)-6-(2-(benzyloxy)ethyl)-5-methyltetrahydro-2H-pyran-2-yl)-2-bromopropanoate
  参考文献：
  名称：

  A Study of Exocyclic Radical Reductions of Polysubstituted Tetrahydropyrans

  摘要：

  Exocyclic radical reductions were thoroughly investigated in the context of the synthesis of polysubstituted tetrahydropyrans, Which are found in numerous macrolides. The radical precursors studied herein were generated by tandem cycloetherification and iodoetherification reactions or, alternatively, by semicyclic acetals substitutions. DFT calculations (BHandHLYP/TZVP) performed at the transition-state level for the hydrogen radical delivery are in good accordance with the experimental data and enabled the identification of important conformational factors that govern the selectivities obtained. This study demonstrates:that both the preferred reactive conformation of the radical and steric interactions with the incoming hydride have to be considered in order to fully rationalize the levels of diastereoselection generated in acyclic free-radical processes.

  DOI：

  10.1021/jo400721e