环己醇,2-[(4-甲氧苯基)甲基]-,(1S,2S)- | 112066-33-8

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯酚醚
• 中文名称: 环己醇,2-[(4-甲氧苯基)甲基]-,(1S,2S)-
• 英文名称: cis-(1S,2S)-(+)-2-(4-methoxybenzyl)-1-cyclohexanol
• 英文别名: (1S,2S)-2-(4-methoxybenzyl)cyclohexan-1-ol；(1S,2S)-2-(4-methoxybenzyl)cyclohexanol；cis-2-(4-Methoxybenzyl)-cyclohexanol；(1S,2S)-2-[(4-methoxyphenyl)methyl]cyclohexan-1-ol
• CAS: 112066-33-8
• 化学式: C₁₄H₂₀O₂
• 分子量: 220.312
• InChiKey: LOYHAUINIBKYQU-JSGCOSHPSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.2
• 重原子数：
  16
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.57
• 拓扑面积：
  29.5
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  环己醇,2-[(4-甲氧苯基)甲基]-,(1S,2S)- 在 ruthenium(IV) oxide 、 sodium periodate 作用下， 以 吡啶 、 四氯化碳 、 水 、 乙腈 为溶剂， 生成 [(1S,2S)-2-(Acetyloxy)cyclohexyl]acetic acid
  参考文献：
  名称：

  Wimmer, Zdenek; Budesinsky, Milos; Macek, Tomas, Collection of Czechoslovak Chemical Communications, 1987, vol. 52, # 9, p. 2326 - 2337

  摘要：

  DOI：
• 作为产物：
  描述：

  (1S,2S)-2-(4-methoxybenzyl)cyclohexyl acetate 在 sodium hydroxide 作用下， 以 乙醇 为溶剂， 反应 4.0h， 生成 环己醇,2-[(4-甲氧苯基)甲基]-,(1S,2S)-
  参考文献：
  名称：

  Hlavsova, Klara; Wimmer, Zdenek; Xanthakis, Epameinondas, Zeitschrift fur Naturforschung, B: Chemical Sciences, 2008, vol. 63, # 6, p. 779 - 784

  摘要：

  DOI：

文献信息

• Synthesis and Structure Assignment of 2-(4-Methoxybenzyl)cyclohexyl β-D-Galactopyranoside Stereoisomers
  作者：David Šaman、Martina Wimmerová、Zdeněk Wimmer

  DOI：10.1135/cccc20061186

  日期：——

  Several promoters were used in the Koenigs-Knorr synthesis of the title alkyl β-D-galactopyranosides, both in their diastereoisomeric forms (5a/5b and 6a/6b), resulting from the synthesis performed with the respective racemic cis and trans isomers of 2-(4-methoxybenzyl)cyclohexan-1-ol, and in their enantiomerically pure forms 5a and 6a, starting only from the (1S,2S)- and (1S,2R)-enantiomers of 2-(4-methoxybenzyl)cyclohexan-1-ol. The aim of the study was to find convenient modification(s) of the Koenigs-Knorr synthesis of alkyl β-D-galactopyranosides from more hindered and more complex 2-substituted cycloalkanols. Separation of the diastereoisomeric compounds using HPLC on a chiral Nucleodex-β-OH column was used to obtain small quantities of all possibly existing enantiomerically pure products for unambiguous structure assignment by NMR analysis. The (1S,2S)- and (1S,2R)- enantiomers of 2-(4-methoxybenzyl)cyclohexan-1-ol (1a and 2a) were prepared by a reduction of 2-(4-methoxybenzyl)cyclohexan-1-one with Saccharomyces cerevisiae in enantiomeric purities: ee = 98.5% ((1S,2S)-enantiomer (1a)), and ee ≥ 99% ((1S,2R)-enantiomer (2a)).

  在Koenigs-Knorr合成法中，使用了几种促进剂来制备所述烷基β-D-半乳糖苷，包括它们的对映异构体形式（5a/5b和6a/6b），这些异构体形式是由于使用相应的外消旋和异构体的2-(4-甲氧基苯甲基)环己醇进行合成而产生的，以及它们的对映纯形式5a和6a，这些只是从(1S,2S)-和(1S,2R)-2-(4-甲氧基苯甲基)环己醇的对映异构体开始制备的。该研究的目的是找到方便的修饰方法，以从更为阻碍和更为复杂的2-取代环烷醇中合成烷基β-D-半乳糖苷。使用手性Nucleodex-β-OH柱的HPLC分离对映异构体化合物，以获得所有可能存在的对映纯产物的少量，以便通过NMR分析进行明确的结构鉴定。通过使用还原2-(4-甲氧基苯甲基)环己酮制备了(1S,2S)-和(1S,2R)-2-(4-甲氧基苯甲基)环己醇(1a和2a)，其对映纯度为：ee=98.5% ((1S,2S)-对映异构体(1a))，ee≥99% ((1S,2R)-对映异构体(2a))。
• Synthesis and Structure Assignment of 2-(4-Methoxybenzyl)cyclohexyl β-D-Glucopyranoside Enantiomers
  作者：David Šaman、Pavel Kratina、Jitka Moravcová、Martina Wimmerová、Zdeněk Wimmer

  DOI：10.1135/cccc20061470

  日期：——

  Glucosylation of the cis- and trans-isomers of 2-(4-methoxybenzyl)cyclohexan-1-ol (1a/1b, 2a/2b, 1a or 2a) was performed to prepare the corresponding alkyl β-D-glucopyranosides, mainly to get analytical data of pure enantiomers of the glucosides (3a-6b), required for subsequent investigations of related compounds with biological activity. One of the employed modifications of the Koenigs-Knorr synthesis resulted in achieving 85-95% yields of pure β-anomers 3a/3b, 4a/4b, 3a or 4a of protected intermediates, with several promoters and toluene as solvent, yielding finally the deprotected products 5a/5b, 6a/6b, 5a or 6a as pure β-anomers. To obtain enantiomerically pure β-anomers of the target structure (3a, 4a, 5a and 6a) for unambiguous structure assignment, an enzymic reduction of 2-(4-methoxybenzyl)cyclohexan-1-one by Saccharomyces cerevisiae whole cells was performed to get (1S,2S)- and (1S,2R)-enantiomers (1a and 2a) of 2-(4-methoxybenzyl)cyclohexan-1-ol. The opposite enantiomers of alkyl β-D-glucopyranosides (5b and 6b) were obtained by separation of the diastereoisomeric mixtures 5a/5b and 6a/6b by chiral HPLC. All stereoisomers of the products (3a-6b) were subjected to a detailed ¹H NMR and ¹³C NMR analysis.

  对2-(4-甲氧基苯基)环己基-1-醇(1a/1b, 2a/2b, 1a或2a)的cis和trans异构体进行葡萄糖基化，制备相应的烷基β-D-葡萄糖苷，主要是为了获得纯对映体的葡萄糖苷(3a-6b)的分析数据，以便后续研究具有生物活性的相关化合物。Koenigs-Knorr合成的一种改进方法之一，通过多种促进剂和甲苯作为溶剂，得到了保护中间体的纯β-异构体3a/3b、4a/4b、3a或4a，收率为85-95%，最终得到去保护产物的纯β-异构体5a/5b、6a/6b、5a或6a。为了获得目标结构(3a、4a、5a和6a)的对映纯β-异构体以进行明确的结构指认，使用Saccharomyces cerevisiae全细胞对2-(4-甲氧基苯基)环己基-1-酮进行酶促还原，获得了(1S,2S)-和(1S,2R)-对映体(1a和2a)的2-(4-甲氧基苯基)环己基-1-醇。通过手性高效液相色谱分离5a/5b和6a/6b的对映异构体混合物，获得了烷基β-D-葡萄糖苷的相反对映体(5b和6b)。所有产物(3a-6b)的立体异构体均经过详细的¹H NMR和¹³C NMR分析。
• Enzymic resolution of 2-substituted cyclohexanols through lipase-mediated esterification
  作者：Zdeněk Wimmer、Vasso Skouridou、Marie Zarevúcka、David Šaman、Fragiskos N. Kolisis

  DOI：10.1016/j.tetasy.2004.11.009

  日期：2004.12

  Several lipases were used for the kinetic resolution of the racemic cis- and trans-isomers of 2-(4-methoxybenzyl)cyclohexanol, by lipase-mediated esterification of the substrates to the corresponding acetate isomers. Conversion of the products and the remaining deracemized substrates into diastereoisomeric esters of 3,3,3-trifluoromethyl-2-methoxy-2-phenylpropanoic acid, their analysis by chiral HPLC and assignment of their absolute configurations through their H-1 and F-19 NMR spectra, were the basis of evaluation of the studied enzymic process. Lipase from Rhizomucor miehei (RML) was found to be the most efficient enzyme regarding enantiomeric excess (ee) and yield of the desired products, while resolution by lipase from Rhizopus arrhizus (RAL) resulted in satisfactory ee and lower yields. (C) 2004 Elsevier Ltd. All rights reserved.
• Application of ionic liquids in enzymic resolution by hydrolysis of cycloalkyl acetates
  作者：Epameinondas Xanthakis、Marie Zarevúcka、David Šaman、Martina Wimmerová、Fragiskos N. Kolisis、Zdeněk Wimmer

  DOI：10.1016/j.tetasy.2006.10.045

  日期：2006.11

  A comparative study was performed in the enzymic resolution of the isomers of 2-(4-methoxybenzyl)cyclohexyl acetates 1 and 2. The investigation consisted in application of three commercially available lipases (Novozyme 435, Lipozyme IM and non-immobilized powdered lipase from Candida antarctica), two ionic liquids (1-butyl-4-methylpyridinium chloride and 1,3-dimethylimidazolinium methyl sulfate), three modifications of the reaction conditions and two respective isomers of the racemic substrate (1 and 2), and resulted in our finding the appropriate conditions to get both of the products, stereoisomers of 2-(4-methoxybenzyl)cyclohexanol (3; 1S,2S) or (5; 1S,2R), and (in some cases) also the stereoisomers of the deracemized substrate (4; 1 R,2R) or (6; 1 R,2S) with high or acceptable enantiomeric purity. (c) 2006 Elsevier Ltd. All rights reserved.