(1R,2S)-trans-2-Phenylcyclohexyl (R)-mandelate | 109462-07-9

• 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: (1R,2S)-trans-2-Phenylcyclohexyl (R)-mandelate
• 英文别名: [(1R,2S)-2-phenylcyclohexyl] (2R)-2-hydroxy-2-phenylacetate
• CAS: 109462-07-9
• 化学式: C₂₀H₂₂O₃
• 分子量: 310.393
• InChiKey: RYVYMIQCNQZBIA-IPMKNSEASA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.4
• 重原子数：
  23
• 可旋转键数：
  5
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.35
• 拓扑面积：
  46.5
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  碘乙烷 、 (1R,2S)-trans-2-Phenylcyclohexyl (R)-mandelate 反应 30.0h， 以83%的产率得到(1R,2S)-trans-2-Phenylcyclohexyl 2(R)-ethoxyphenylacetate
  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：

  (1R,2S)-trans-2-phenylcyclohexanol 、 D-扁桃酸 在 对甲苯磺酸 作用下， 以 甲苯 为溶剂， 以76%的产率得到(1R,2S)-trans-2-Phenylcyclohexyl (R)-mandelate
  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

• Highly diastereoselective reduction and alkylation of (1R,2S)-trans-2-phenylcyclohexanol phenylglyoxylate and pyruvate using hindered hydrides and alkyl aluminates
  作者：Gérard Boireau、Alain Deberly、André Loupy、Daphné Monteux

  DOI：10.1016/s0040-4039(99)01415-x

  日期：1999.9

  (1R,2S)-trans-2-Phenylcyclohexanol phenylglyoxylate and pyruvate are reduced with modest to excellent diastereoselectivities (30–99%) by reaction with bulky lithium trialkoxyaluminohydrides and alkylated with excellent diastereoselectivities (88–100%) by addition of hindered lithium alkoxytrialkylaluminates.

  （1 R，2 S）-反式-2-苯基环己醇苯乙醛酸酯和丙酮酸通过与庞大的三烷氧基铝氢化锂反应而被还原成中等至优异的非对映选择性（30–99％），并通过添加受阻而被烷基化以优异的非对映选择性（88–100％）烷氧基三烷基铝酸锂。
• WHITESELL J. K.; LAWRENCE R. M., CHIMIA, 40,(1986) N 9, 318-321
  作者：WHITESELL J. K.、 LAWRENCE R. M.

  DOI：——

  日期：——
• 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.