cis-1-(3-hydroxypropyl)-2-methoxycyclohexanol | 134210-03-0

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: cis-1-(3-hydroxypropyl)-2-methoxycyclohexanol
• 英文别名: (1R,2R)-1-(3-hydroxypropyl)-2-methoxycyclohexan-1-ol
• CAS: 134210-03-0；134210-05-2
• 化学式: C₁₀H₂₀O₃
• 分子量: 188.267
• InChiKey: NHUOPUCYKMHCGO-NXEZZACHSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.6
• 重原子数：
  13
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  49.7
• 氢给体数：
  2
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  cis-1-(3-hydroxypropyl)-2-methoxycyclohexanol 在 4-二甲氨基吡啶 、 三乙胺 、 对甲苯磺酰氯 作用下， 以 二氯甲烷 为溶剂， 反应 16.0h， 以73%的产率得到(5S,6S)-6-methoxy-1-oxaspiro[4.5]decane
  参考文献：
  名称：

  Electrostatic modulation of hydroxyl group ionization in acidic media. Evidence for the competitive operation of intramolecular SN2 reactions

  摘要：

  The acid-catalyzed cyclodehydration of the cis and trans isomers of 2-substituted 1-(3-hydroxypropyl)cyclohexanols results in the formation of spirocyclic tetrahydrofurans. The stereochemical course of these reactions is highly varied, ranging from a dominant preference for retention when R = OCH3 to modestly favored inversion when R = CH3. Experiments with O-18-labeled diols show that in the methoxyl series most of the isotope is retained irrespective of relative stereochemistry. On the other hand, the pair of phenyl-substituted isomers responds by losing approximately 50% of the label. The isotopic level in the product erodes further when R = CH3. The stereochemical and isotopic labeling results are interpreted in terms of competing intramolecular S(N)2 and classical S(N)1 pathways. The extent to which cooperative nucleophilic attack with loss of the primary hydroxyl is facilitated reaches a maximum in the methoxyl-substituted diols, as a consequence of electrostatic inhibition of tertiary carbocation formation. As this effect is progressively lessened, the percentage of S(N)1 response rises. At no time, however, do the stereoisomeric carbocations interconvert conformationally prior to cyclization.

  DOI：

  10.1021/ja00049a014
• 作为产物：
  描述：

  (1S*,2S*)-1-allyl-2-methoxycyclohexan-1-ol 在 sodium hydroxide 、 硼烷四氢呋喃络合物 、 双氧水 作用下， 生成 cis-1-(3-hydroxypropyl)-2-methoxycyclohexanol
  参考文献：
  名称：

  Electrostatic modulation of hydroxyl group ionization in acidic media. Evidence for the competitive operation of intramolecular SN2 reactions

  摘要：

  The acid-catalyzed cyclodehydration of the cis and trans isomers of 2-substituted 1-(3-hydroxypropyl)cyclohexanols results in the formation of spirocyclic tetrahydrofurans. The stereochemical course of these reactions is highly varied, ranging from a dominant preference for retention when R = OCH3 to modestly favored inversion when R = CH3. Experiments with O-18-labeled diols show that in the methoxyl series most of the isotope is retained irrespective of relative stereochemistry. On the other hand, the pair of phenyl-substituted isomers responds by losing approximately 50% of the label. The isotopic level in the product erodes further when R = CH3. The stereochemical and isotopic labeling results are interpreted in terms of competing intramolecular S(N)2 and classical S(N)1 pathways. The extent to which cooperative nucleophilic attack with loss of the primary hydroxyl is facilitated reaches a maximum in the methoxyl-substituted diols, as a consequence of electrostatic inhibition of tertiary carbocation formation. As this effect is progressively lessened, the percentage of S(N)1 response rises. At no time, however, do the stereoisomeric carbocations interconvert conformationally prior to cyclization.

  DOI：

  10.1021/ja00049a014

文献信息

• π-Facial Diastereoselection in the 1,2-Addition of Allylmetal Reagents to 2-Methoxycyclohexanone and Tetrahydrofuranspiro-(2-cyclohexanone)
  作者：Leo A. Paquette、Paul C. Lobben

  DOI：10.1021/ja9536835

  日期：1996.1.1

  stereochemical course of the 1,2-addition of several allylmetal reagents and of the Normant Grignard [ClMgO(CH2)3MgCl] to 2-methoxycyclohexanone and tetrahydrofuranspiro-(2-cyclohexanone) has been determined. In four of the six substrates examined, a 4-tert-butyl group is present to serve as a conformational anchor. The neighboring methoxyl substituent is shown to be capable of engaging effectively in

  已经确定了几种烯丙基金属试剂和 Normant Grignard [ClMgO(CH2)3MgCl] 的 1,2-加成到 2-甲氧基环己酮和四氢呋喃螺-(2-环己酮) 的立体化学过程。在检测的六种底物中的四种中，存在一个 4-叔丁基作为构象锚。相邻的甲氧基取代基显示出能够有效参与螯合，尽管特殊情况可能另有规定。涉及烯丙基试剂作为水溶液中的亲核试剂的实验表明，水的存在不会抑制螯合控制的操作，这通常大大超过在无水介质中使用相应的镁、铈和铬试剂所能达到的效果。
• PAQUETTE, LEO A.;NEGRI, JOANNA T., J. AMER. CHEM. SOC., 113,(1991) N3, C. 5072-5073
  作者：PAQUETTE, LEO A.、NEGRI, JOANNA T.

  DOI：——

  日期：——
• Raquette, Leo A.; Negri, Joanna T., Journal of the American Chemical Society, 1991, vol. 113, # 13, p. 5072 - 5073
  作者：Raquette, Leo A.、Negri, Joanna T.

  DOI：——

  日期：——