(S)-O-Methylmandelic acid derivative of (-)-menthol | 123642-96-6

• 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: (S)-O-Methylmandelic acid derivative of (-)-menthol
• 英文别名: (1R,2S,5R,2'S)-menthyl 2'-methoxy-2'-phenylacetate；(1R,2S,5R)-Menthyl (S)-2-methoxyphenylacetate；(-)-Menthyl (+)-(S)-O-methylmandelate；(S)-O-Methyl-mandelsaeure-(R)-menthylester；[(1R,2S,5R)-5-methyl-2-propan-2-ylcyclohexyl] (2S)-2-methoxy-2-phenylacetate
• CAS: 123642-96-6
• 化学式: C₁₉H₂₈O₃
• 分子量: 304.43
• InChiKey: IEMYHZQLRMVTQY-SPUZQDLCSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.2
• 重原子数：
  22
• 可旋转键数：
  6
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.63
• 拓扑面积：
  35.5
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为产物：
  描述：

  l-menthyl phenylglyoxylate 在 dirhodium tetraacetate 三乙胺 作用下， 以 二氯甲烷 、 甲苯 为溶剂， 生成 (S)-O-Methylmandelic acid derivative of (-)-menthol
  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

• Pigments of Fungi. LXVI. The Gentiobiosides of (R)- and (S)-Torosachrysone from Australian Toadstools and Methods for Assaying the Enantiomeric Purity of Natural Torosachrysone
  作者：Melvyn Gill、Simon Saubern、Jin Yu

  DOI：10.1071/ch00038

  日期：——

  The diastereoisomeric 8-O--b-gentiobiosides (2) and (10)of (S)- and (R)-torosachrysone (1)and (11), respectively, are isolated in admixture to varying degrees fromtoadstools belonging to the genera Cortinarius andDermocybe. (R)-Torosachrysone (11)is characterized for the first time from a fungus and spectroscopic andchromatographic methods are described that show that torosachrysone, as itoccurs in

  (S)-和 (R)-torosachrysone (1) 和 (11) 的非对映异构体 8-O--b-龙胆二苷 (2) 和 (10) 分别以不同程度的混合物从属于该属的毒菌中分离出来Cortinarius和Dermocybe。(R)-Torosachrysone (11) 首次从一种真菌中表征，并描述了光谱和色谱方法，表明 Torosachrysone，因为它存在于几种真菌中，是非手性的，其立体化学组成是物种依赖性的。
• Nuclear magnetic resonance nonequivalence of diastereomeric esters of .alpha.-substituted phenylacetic acids for the determination of stereochemical purity
  作者：James A. Dale、Harry S. Mosher

  DOI：10.1021/ja01016a024

  日期：1968.7
• Novel sponge-derived amino acids. 11. The entire absolute stereochemistry of the bengamides
  作者：Madeline Adamczeski、Emilio Quinoa、Phillip Crews

  DOI：10.1021/jo00288a039

  日期：1990.1
• Conformational Structure and Dynamics of Arylmethoxyacetates: DNMR Spectroscopy and Aromatic Shielding Effect
  作者：Sh. K. Latypov、J. M. Seco、E. Quinoa、R. Riguera

  DOI：10.1021/jo00108a008

  日期：1995.2

  The ground state conformational geometry and energy of esters of (R)- and (S)-arylmethoxyacetic acids were evaluated from low temperature H-1 and C-13 NMR spectra and by means of MM, AM1, and aromatic shielding effect calculations. In solution, the title compounds are constituted by two rotamers in equilibrium. Rotamer ap has the C-alpha-O and C=O bonds antiperiplanar and rotamer sp (lower in energy by 0.4-1.1 kcal/mol) has these bonds synperiplanar. In both the ap and the sp the aryl ring is ca. perpendicular to the C=O bond and coplanar with the CalphaH bond. Their relative populations and its temperature dependence evaluated by DNMR spectra are in agreement with the stereoselectivity reported for Diels-Alder reactions of dienyl-AMAA esters and support the ''perpendicular model'' proposed to account for that stereoselectivity. For conformations in which the aryl ring shields the alcohol moiety of the ester, calculated ring current shielding increments compare well with experimental shift values obtained from low-temperature NMR spectra and agree with the conformational model used in the Mislow-Dale-Mosher-Trost method for chiral recognition by NMR.
• ADAMCZESKI, MADELINE;QUINOA, EMILIO;CREWS, PHILLIP, J. ORG. CHEM., 55,(1990) N, C. 240-242
  作者：ADAMCZESKI, MADELINE、QUINOA, EMILIO、CREWS, PHILLIP

  DOI：——

  日期：——