all-cis-3,5-dihydroxy-4-methyl-1-(methoxycarbonyl)cyclohexane | 326598-92-9

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: all-cis-3,5-dihydroxy-4-methyl-1-(methoxycarbonyl)cyclohexane
• CAS: 326598-92-9
• 化学式: C₉H₁₆O₄
• 分子量: 188.224
• InChiKey: YQRQCQPMSOFSPY-KVFPUHGPSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -0.07
• 重原子数：
  13.0
• 可旋转键数：
  1.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.89
• 拓扑面积：
  66.76
• 氢给体数：
  2.0
• 氢受体数：
  4.0

反应信息

• 作为反应物：
  描述：

  all-cis-3,5-dihydroxy-4-methyl-1-(methoxycarbonyl)cyclohexane 在 甲醇 、 phosphate buffer 、 Pseudomonas cepacia lipase 、 三氟甲磺酸三甲基硅酯 作用下， 以 二氯甲烷 、 乙腈 为溶剂， 反应 45.5h， 生成 (1R,3S,4S,5R)-3-acetoxy-5-hydroxy-4-methyl-1-(methoxycarbonyl)cyclohexane
  参考文献：
  名称：

  Asymmetrization of all-cis-3,5-dihydroxy-1-(methoxycarbonyl)cyclohexane and of the 4-methyl and 4-ethyl substituted homologues

  摘要：

  Enantiomerically pure mono acylated derivatives of cis,cis-3, 5-dihydroxy-1-(methoxycarbonyl)cyclohexane 1, all-cis-3,5-dihydroxy-4-methyl-1-(methoxycarbonyl)cyclohexane 2 and all-cis-3,5-dihydroxy-4-ethyl-1-(methoxycarbonyl)cyclohexane 3 were obtained upon lipase catalyzed asymmetrization. PPL-catalyzed transesterification of 1 with vinyl acetate led in high yield to the (S)-monoacetate (+)-13. With substrates 2 and 3 this process was slower and gave the (R)-monoacetates (-)-14 and (-)-15; the best results were obtained with SAM II lipase. On the other hand, enantiotoposelective hydrolysis of their diacetates and especially dibutyrates gave useful results only for the 4-substituted substrates and produced the (S)-monoesters. (C) 2000 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0957-4166(00)00339-6
• 作为产物：
  描述：

  3,5-二羟基-4-甲基苯甲酸甲酯 在 Rh/Al₂O₃ 氢气 、 溶剂黄146 作用下， 以 甲醇 为溶剂， 105.0 ℃ 、13.17 MPa 条件下， 反应 22.0h， 以62%的产率得到all-cis-3,5-dihydroxy-4-methyl-1-(methoxycarbonyl)cyclohexane
  参考文献：
  名称：

  Asymmetrization of all-cis-3,5-dihydroxy-1-(methoxycarbonyl)cyclohexane and of the 4-methyl and 4-ethyl substituted homologues

  摘要：

  Enantiomerically pure mono acylated derivatives of cis,cis-3, 5-dihydroxy-1-(methoxycarbonyl)cyclohexane 1, all-cis-3,5-dihydroxy-4-methyl-1-(methoxycarbonyl)cyclohexane 2 and all-cis-3,5-dihydroxy-4-ethyl-1-(methoxycarbonyl)cyclohexane 3 were obtained upon lipase catalyzed asymmetrization. PPL-catalyzed transesterification of 1 with vinyl acetate led in high yield to the (S)-monoacetate (+)-13. With substrates 2 and 3 this process was slower and gave the (R)-monoacetates (-)-14 and (-)-15; the best results were obtained with SAM II lipase. On the other hand, enantiotoposelective hydrolysis of their diacetates and especially dibutyrates gave useful results only for the 4-substituted substrates and produced the (S)-monoesters. (C) 2000 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0957-4166(00)00339-6

文献信息

• A Convenient, Large Scale Synthesis of<i>trans</i>-(+)-Sobrerol
  作者：Qiuan Wang、Yanlin Li、Qingqi Chen

  DOI：10.1081/scc-120021040

  日期：2003.7

  A convenient and highly efficient synthesis of optically pure trans(+)-sobrerol (1), starting from methyl 3,5-dihydroxy-4-methyl benzoate 2 in 8 steps with overall yield 26%, is reported. The key intermediate 4 is prepared in remarkably high yield by selectively esterification of 3 using lipase as catalyst. A critical step to stereoselectively inverse the configuration of 7 is realized under Mistunobu conditions.
• Asymmetrization of all-cis-3,5-dihydroxy-1-(methoxycarbonyl)cyclohexane and of the 4-methyl and 4-ethyl substituted homologues
  作者：Yurui Zhao、Yusheng Wu、Pierre De Clercq、Maurits Vandewalle、Philippe Maillos、Jean-Claude Pascal

  DOI：10.1016/s0957-4166(00)00339-6

  日期：2000.10

  Enantiomerically pure mono acylated derivatives of cis,cis-3, 5-dihydroxy-1-(methoxycarbonyl)cyclohexane 1, all-cis-3,5-dihydroxy-4-methyl-1-(methoxycarbonyl)cyclohexane 2 and all-cis-3,5-dihydroxy-4-ethyl-1-(methoxycarbonyl)cyclohexane 3 were obtained upon lipase catalyzed asymmetrization. PPL-catalyzed transesterification of 1 with vinyl acetate led in high yield to the (S)-monoacetate (+)-13. With substrates 2 and 3 this process was slower and gave the (R)-monoacetates (-)-14 and (-)-15; the best results were obtained with SAM II lipase. On the other hand, enantiotoposelective hydrolysis of their diacetates and especially dibutyrates gave useful results only for the 4-substituted substrates and produced the (S)-monoesters. (C) 2000 Elsevier Science Ltd. All rights reserved.