(1S,2R)-trans-2-Phenylcyclohexyl 2-oxophenylacetate | 170421-68-8

• 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: (1S,2R)-trans-2-Phenylcyclohexyl 2-oxophenylacetate
• 英文别名: [(1S,2R)-2-phenylcyclohexyl] 2-oxo-2-phenylacetate
• CAS: 170421-68-8
• 化学式: C₂₀H₂₀O₃
• 分子量: 308.377
• InChiKey: XGBFDQAWLIRJBT-MSOLQXFVSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.9
• 重原子数：
  23
• 可旋转键数：
  5
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.3
• 拓扑面积：
  43.4
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (1S,2R)-trans-2-Phenylcyclohexyl 2-oxophenylacetate 在 三乙胺 作用下， 以 二氯甲烷 、 甲苯 为溶剂， 生成 (1S,2R)-trans-2-Phenylcyclohexyl 2-diazophenylacetate
  参考文献：
  名称：

  Diastereoselectivity in the O-H Insertion Reactions of Rhodium Carbenoids Derived from Phenyldiazoacetates of Chiral Alcohols. Preparation of .alpha.-Hydroxy and .alpha.-Alkoxy Esters

  摘要：

  A series of phenyldiazoacetates 3 derived from enantiomerically pure alcohols ((-)-borneol, (+)menthol, (-)-menthol, (-)-8-phenylmenthol, (-)-trans-2-phenylcyclohexanol, (+)-trans-2-phenyl-cyclohexanol, and (-)10-(dicyclohexylsulfamoyl)-D-isoborneol) were prepared from the corresponding alpha-keto esters 1 by way of the tosylhydrazones 2. Rhodium(II)-catalyzed decomposition of the diazoacetates 3 in the presence of water or alcohols resulted in carbenoid O-H insertion reactions to give the corresponding 2-hydroxy- or 2-alkoxyphenylacetates in good yield, but with varying degrees of diastereoselectivity. A range of rhodium(II) and other metal catalysts were investigated, with rhodium(II) acetate and rhodium(II) acetamide giving the best results. The stereochemistry of the major diastereomer was proved in most cases by independent synthesis from a mandelic acid derivative of known configuration. Possible mechanisms are discussed.

  DOI：

  10.1021/jo00119a023
• 作为产物：
  描述：

  氧代(苯基)乙酰氯 、 (1S,2R)-(+)-反-2-苯基-1-环己醇 在 对甲苯磺酸 作用下， 以 甲苯 为溶剂， 以83%的产率得到(1S,2R)-trans-2-Phenylcyclohexyl 2-oxophenylacetate
  参考文献：
  名称：

  Diastereoselectivity in the O-H Insertion Reactions of Rhodium Carbenoids Derived from Phenyldiazoacetates of Chiral Alcohols. Preparation of .alpha.-Hydroxy and .alpha.-Alkoxy Esters

  摘要：

  A series of phenyldiazoacetates 3 derived from enantiomerically pure alcohols ((-)-borneol, (+)menthol, (-)-menthol, (-)-8-phenylmenthol, (-)-trans-2-phenylcyclohexanol, (+)-trans-2-phenyl-cyclohexanol, and (-)10-(dicyclohexylsulfamoyl)-D-isoborneol) were prepared from the corresponding alpha-keto esters 1 by way of the tosylhydrazones 2. Rhodium(II)-catalyzed decomposition of the diazoacetates 3 in the presence of water or alcohols resulted in carbenoid O-H insertion reactions to give the corresponding 2-hydroxy- or 2-alkoxyphenylacetates in good yield, but with varying degrees of diastereoselectivity. A range of rhodium(II) and other metal catalysts were investigated, with rhodium(II) acetate and rhodium(II) acetamide giving the best results. The stereochemistry of the major diastereomer was proved in most cases by independent synthesis from a mandelic acid derivative of known configuration. Possible mechanisms are discussed.

  DOI：

  10.1021/jo00119a023

文献信息

• Chiral induction in photochemical reactions. 14.
  作者：Helmut Buschmann、Norbert Hoffmann、Hans-Dieter Scharf

  DOI：10.1016/s0957-4166(00)80038-5

  日期：1991.1

  structural variations of a chiral auxiliary and its influence of the diastereomeric excess in the photochemical oxetane formation in correspondance to the Ugi/Ruch concept. For this purpose we use a Linear Free Energy Relationship (LFER) which we have adjusted to reaction (2) in order to obtain quantitative information about the selectivity of this reaction on the basis of special parameters of the auxiliary

  为了评价化学计量的不对称合成，对于合成化学家而言，重要的是获得有关手性助剂的那些在特定反应中造成非对映异构体过量的结构元素的信息。此外，期望具有关于手性转移机理的详细知识。在本文中，建立了一种经验关系，用于与手性助剂的结构变化及其对非对映体过量在光化学氧杂环丁烷形成中的影响（与Ugi / Ruch概念相对应）的相关性。为此，我们使用线性自由能关系（LFER），我们已对其进行了调整以适应反应（2），以便根据所用助剂的特殊参数获得有关该反应选择性的定量信息。
• Diastereoselectivity in the O-H Insertion Reactions of Rhodium Carbenoids Derived from Phenyldiazoacetates of Chiral Alcohols. Preparation of .alpha.-Hydroxy and .alpha.-Alkoxy Esters
  作者：Enrique Aller、David S. Brown、Geoffrey G. Cox、David J. Miller、Christopher J. Moody

  DOI：10.1021/jo00119a023

  日期：1995.7

  A series of phenyldiazoacetates 3 derived from enantiomerically pure alcohols ((-)-borneol, (+)menthol, (-)-menthol, (-)-8-phenylmenthol, (-)-trans-2-phenylcyclohexanol, (+)-trans-2-phenyl-cyclohexanol, and (-)10-(dicyclohexylsulfamoyl)-D-isoborneol) were prepared from the corresponding alpha-keto esters 1 by way of the tosylhydrazones 2. Rhodium(II)-catalyzed decomposition of the diazoacetates 3 in the presence of water or alcohols resulted in carbenoid O-H insertion reactions to give the corresponding 2-hydroxy- or 2-alkoxyphenylacetates in good yield, but with varying degrees of diastereoselectivity. A range of rhodium(II) and other metal catalysts were investigated, with rhodium(II) acetate and rhodium(II) acetamide giving the best results. The stereochemistry of the major diastereomer was proved in most cases by independent synthesis from a mandelic acid derivative of known configuration. Possible mechanisms are discussed.