(1'R,2'S,5'R)-2'-(1-methyl-1-phenylethyl)-5'-methylcyclohexyl (R)-2-hydroxyphenylacetate | 88292-43-7

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 异戊烯醇脂质
• 英文名称: (1'R,2'S,5'R)-2'-(1-methyl-1-phenylethyl)-5'-methylcyclohexyl (R)-2-hydroxyphenylacetate
• 英文别名: (1R,3R,4S)-8-phenylmenthyl (R)-mandelate；1R,2S,5R,R-(-)-8-phenylmenthyl mandelate；(1R,2S,5R)-8-Phenylmenthyl (R)-mandelate；[(1R,2S,5R)-5-methyl-2-(2-phenylpropan-2-yl)cyclohexyl] (2R)-2-hydroxy-2-phenylacetate
• CAS: 88292-43-7
• 化学式: C₂₄H₃₀O₃
• 分子量: 366.5
• InChiKey: PLBYOXDTQIUGGQ-BRKWEVRTSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.1
• 重原子数：
  27
• 可旋转键数：
  6
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.46
• 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：

  2-碘代丙烷 、 (1'R,2'S,5'R)-2'-(1-methyl-1-phenylethyl)-5'-methylcyclohexyl (R)-2-hydroxyphenylacetate 在 silver(l) oxide 作用下， 反应 30.0h， 以58%的产率得到(1R,3R,4S)-8-phenylmenthyl (R)-2-isopropoxy-2-phenylacetate
  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：

  (-)-8-苯基薄荷醇 在 rhodium(II) acetate dimer 水 、 对甲苯磺酸 、 三乙胺 作用下， 以 二氯甲烷 、 甲苯 为溶剂， 生成 (1'R,2'S,5'R)-2'-(1-methyl-1-phenylethyl)-5'-methylcyclohexyl (R)-2-hydroxyphenylacetate
  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

• Asymmetric induction. Reduction, nucleophilic addition to, and ene reactions of chiral α-ketoesters
  作者：James K. Whitesell、Don Deyo、Apurba Bhattacharya

  DOI：10.1039/c39830000802

  日期：——

  Ketoesters of 8-phenylmenthol undergo reduction with potassium tri-isopropoxyborohydride, addition of Grignard reagents, and ene reactions with asymmetric induction levels of 90% and above.

  用三异丙氧基硼氢化钾还原8-苯基薄荷醇的酮酸酯，添加格氏试剂，以及不对称诱导水平达90％或更高的烯类反应。
• Diastereoselectivity in the O - H Insertion Reactions of Carbenoids Derived from Phenyldiazoacetates of Chiral Alcohols. II. Comparison of Rhodium(II)- and Acid-Mediated Reactions
  作者：David J. Miller、Christopher J. Moody、C. Neil Morffitt

  DOI：10.1071/c98159

  日期：——

  Rhodium(II)- or acid-mediated decomposition of 2-diazo-2-phenylacetates of chiral alcohols in the presence of various hydroxylic compounds (ROH) results in the diastereoselective formation of 2- hydroxy-, 2-alkoxy- or 2-trialkylsiloxy-2-phenylacetates, with the acid-mediated process giving the higher diastereoselectivity.

  铑（II）或酸介导的手性醇的 2-重氮-2-苯基乙酸酯的分解 手性醇的 2-重氮-2-苯基乙酸酯在各种羟基化合物 (ROH) 存在下进行分解，结果是 非对映选择性地形成 2-羟基、2-烷氧基或 2-三烷基硅氧基-2-苯基乙酸酯的非对映选择性，其中以酸为介导的过程具有较高的非对映选择性。 非对映选择性更高。
• Asymmetric syntheses with a new optically active perhydronaphthalene based chiral auxiliary
  作者：David P.G. Hamon、Jeffrey W. Holman、Ralph A. Massy-Westropp

  DOI：10.1016/s0040-4020(01)80228-3

  日期：——

  (1R,4aS,8S,8aS)-8-(5′-Methoxy-2′-methylphenyl)-8-methyldecahydro-1-naphthalenol 3a is a highly efficient chiral auxiliary in the Diels-Alder addition of its acrylate ester 5 and in the DIBAL-H and Grignard reactions of its phenylglyoxylate ester 7.

  （1 R，4a S，8 S，8a S）-8-（5'-甲氧基-2'-甲基苯基）-8-甲基十氢-1-萘3a是Diels-Alder添加的高效手性助剂丙烯酸酯5以及在DIBAL-H和Grignard反应中的苯乙醛酸酯7。
• Rhodium-catalyzed reactions of arylbismuth and aryllead reagents with a chiral glyoxylate hydrate in air and water: water-promoted diastereoselectivity enhancement
  作者：Rui Ding、Cheng-Sheng Ge、Yong-Jun Chen、Dong Wang、Chao-Jun Li

  DOI：10.1016/s0040-4039(02)01814-2

  日期：2002.10

  In the presence of a rhodium catalyst, a chiral glyoxylate hydrate reacts with arylbismuth and aryllead reagents in water and under an atmosphere of air to give the corresponding addition products in high yields. The diastereoselectivities of the reactions were dramatically improved by using water as the solvent. (C) 2002 Elsevier Science Ltd. All rights reserved.
• Diastereoselective reduction of an α-keto-ester derived from (−)-8-phenylmenthol: A 4-step synthesis of R-Halostachine analogue.
  作者：Arlette Solladié-Cavallo、Mohamed Bencheqroun

  DOI：10.1016/s0957-4166(00)82014-5

  日期：1991.1

  An efficient (80% total yield) 4-step synthesis of a 94% e.e. R-(-)-Halostachine analogue is described. The method offers the possibility to introduce various substituents onto the aromatic ring and various alkyl groups on the amine. A one-step and high yield (almost-equal-to 100%) conversion of esters into amides is presented.