[(2R,4R)-4-phenoxypentan-2-yl] 2-diazoacetate | 470475-61-7

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯酚醚
• 英文名称: [(2R,4R)-4-phenoxypentan-2-yl] 2-diazoacetate
• CAS: 470475-61-7
• 化学式: C₁₃H₁₆N₂O₃
• 分子量: 248.282
• InChiKey: YZVCIMBCYTZSCL-GHMZBOCLSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.3
• 重原子数：
  18
• 可旋转键数：
  7
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.38
• 拓扑面积：
  37.5
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  [(2R,4R)-4-phenoxypentan-2-yl] 2-diazoacetate 在 dirhodium tetraacetate 作用下， 以 二氯甲烷 为溶剂， 反应 3.0h， 生成 (3R,5R,8S)-3,5-dimethyl-2,6-dioxabicyclo[6.5.0]trideca-1(13),9,11-trien-7-one 、 (3R,5R,8R)-3,5-dimethyl-2,6-dioxabicyclo[6.5.0]trideca-1(13),9,11-trien-7-one
  参考文献：
  名称：

  “Chiral Perturbation Factor” Approach Reveals Importance of Entropy Term in Stereocontrol of the 2,4-Pentanediol-Tethered Reaction

  摘要：

  The stereocontrol mechanism of the 2, 4-pentanediol (PD)-tethered reaction was studied in detail using a reaction system consisting of phenyl and rhodium carbenoid moieties. Different tethers were examined to analyze the effects of the methyl groups on the PD tether. Among the reactions with these tethers, the PD tether achieves an unmeasurably high stereoselectivity in a diastereomeric ratio of > 500. Another tether showing a high but measurable stereoselectivity in a ratio of 41 is mostly controlled by the entropy term. To clarify the role of the methyl groups on the chiral tethers, which are the origin of the stereocontrol, the "chiral perturbation factor" is introduced. This parameter is defined as the rate of a chiral reaction relative to that of an achiral reference reaction. By analyzing the temperature dependence of the chiral perturbation factors for different chiral-tethered reactions, high potentials of the PD-tethered reaction in its stereocontrol are concluded to be due to the entropy term.

  DOI：

  10.1021/jo025937s
• 作为产物：
  描述：

  (2S,4R)-4-phenoxypentan-2-ol 在 氢氧化钾 、 对甲苯磺酰叠氮 、 三乙胺 、 三苯基膦 、 偶氮二甲酸二乙酯 作用下， 以 四氢呋喃 、 乙醇 、 二氯甲烷 、 乙腈 为溶剂， 反应 2.0h， 生成 [(2R,4R)-4-phenoxypentan-2-yl] 2-diazoacetate
  参考文献：
  名称：

  “Chiral Perturbation Factor” Approach Reveals Importance of Entropy Term in Stereocontrol of the 2,4-Pentanediol-Tethered Reaction

  摘要：

  The stereocontrol mechanism of the 2, 4-pentanediol (PD)-tethered reaction was studied in detail using a reaction system consisting of phenyl and rhodium carbenoid moieties. Different tethers were examined to analyze the effects of the methyl groups on the PD tether. Among the reactions with these tethers, the PD tether achieves an unmeasurably high stereoselectivity in a diastereomeric ratio of > 500. Another tether showing a high but measurable stereoselectivity in a ratio of 41 is mostly controlled by the entropy term. To clarify the role of the methyl groups on the chiral tethers, which are the origin of the stereocontrol, the "chiral perturbation factor" is introduced. This parameter is defined as the rate of a chiral reaction relative to that of an achiral reference reaction. By analyzing the temperature dependence of the chiral perturbation factors for different chiral-tethered reactions, high potentials of the PD-tethered reaction in its stereocontrol are concluded to be due to the entropy term.

  DOI：

  10.1021/jo025937s

文献信息

• “Chiral Perturbation Factor” Approach Reveals Importance of Entropy Term in Stereocontrol of the 2,4-Pentanediol-Tethered Reaction
  作者：Takahiro Tei、Yasuhiro Sato、Kazutake Hagiya、Akira Tai、Tadashi Okuyama、Takashi Sugimura

  DOI：10.1021/jo025937s

  日期：2002.9.1

  The stereocontrol mechanism of the 2, 4-pentanediol (PD)-tethered reaction was studied in detail using a reaction system consisting of phenyl and rhodium carbenoid moieties. Different tethers were examined to analyze the effects of the methyl groups on the PD tether. Among the reactions with these tethers, the PD tether achieves an unmeasurably high stereoselectivity in a diastereomeric ratio of > 500. Another tether showing a high but measurable stereoselectivity in a ratio of 41 is mostly controlled by the entropy term. To clarify the role of the methyl groups on the chiral tethers, which are the origin of the stereocontrol, the "chiral perturbation factor" is introduced. This parameter is defined as the rate of a chiral reaction relative to that of an achiral reference reaction. By analyzing the temperature dependence of the chiral perturbation factors for different chiral-tethered reactions, high potentials of the PD-tethered reaction in its stereocontrol are concluded to be due to the entropy term.