[(2R,4S)-4-phenoxypentan-2-yl] 2-diazoacetate | 201848-52-4

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯酚醚
• 英文名称: [(2R,4S)-4-phenoxypentan-2-yl] 2-diazoacetate
• CAS: 201848-52-4
• 化学式: C₁₃H₁₆N₂O₃
• 分子量: 248.282
• InChiKey: YZVCIMBCYTZSCL-WDEREUQCSA-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,4S)-4-phenoxypentan-2-yl] 2-diazoacetate 在 dirhodium tetraacetate 作用下， 以 二氯甲烷 、 氯仿 为溶剂， 生成 (1R,3S,5R,8S,11S)-3,5-dimethyl-7-oxo-2,6-dioxatricyclo[9.2.2.01,8]pentadeca-9,14-diene-12,12,13,13-tetracarbonitrile
  参考文献：
  名称：

  光学活性 Tropilidenes 的首次不对称合成。使用 2,4-戊二醇作为手性连接桥将重氮酯高度区域和非对映差异加成到芳香环上

  摘要：

  在完全区域和立体分化下，使用 2,4-戊二醇作为手性连接桥，通过重氮酯与芳环的环加成反应制备光学活性三亚苯基。

  DOI：

  10.1246/cl.1998.45
• 作为产物：
  描述：

  (4S,2R)-4-phenoxypentane-2-ol 在 对甲苯磺酰叠氮 、 三乙胺 作用下， 以 二氯甲烷 、 乙腈 为溶剂， 生成 [(2R,4S)-4-phenoxypentan-2-yl] 2-diazoacetate
  参考文献：
  名称：

  Entropy-Controlled Asymmetric Synthesis. How Differential Activation Entropy Is Induced in Chiral Tethered Reactions

  摘要：

  [GRAPHICS]Kinetic measurements to determine effective molarities of intramolecular reactions using 2,4-pentanediol and related tethers showed that methyl groups on the tether accelerate the major diastereomeric process but decelerate the minor process. The efficient promotion of stereocontrol is suggested to be due to chiral perturbation of the reaction rate through the entropy term, The conformation of the encounter complex of the reagent and reactant moieties was deduced by stereochemical analysis of the intramolecular adducts.

  DOI：

  10.1021/ol006741m

文献信息

• Entropy-Controlled Asymmetric Synthesis. How Differential Activation Entropy Is Induced in Chiral Tethered Reactions
  作者：Takashi Sugimura、Kazutake Hagiya、Yasuhiro Sato、Takahiro Tei、Akira Tai、Tadashi Okuyama

  DOI：10.1021/ol006741m

  日期：2001.1.1

  [GRAPHICS]Kinetic measurements to determine effective molarities of intramolecular reactions using 2,4-pentanediol and related tethers showed that methyl groups on the tether accelerate the major diastereomeric process but decelerate the minor process. The efficient promotion of stereocontrol is suggested to be due to chiral perturbation of the reaction rate through the entropy term, The conformation of the encounter complex of the reagent and reactant moieties was deduced by stereochemical analysis of the intramolecular adducts.
• “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.
• The First Asymmetric Synthesis of Optically Active Tropilidenes. Highly Regio- and Diastereo-differentiating Addition of Diazo Ester to Aromatic Ring Using 2,4-Pentanediol as Chiral Linking Bridge
  作者：Takashi Sugimura、Shinya Nagano、Akira Tai

  DOI：10.1246/cl.1998.45

  日期：1998.1

  Optically active tropilidenes were prepared by cycloaddition of a diazo ester to an aromatic ring using 2,4-pentanediol as a chiral linking bridge under complete regio- and stereo-differentiations.

  在完全区域和立体分化下，使用 2,4-戊二醇作为手性连接桥，通过重氮酯与芳环的环加成反应制备光学活性三亚苯基。