(1S,3R,6R,R_S)-1-(Benzyloxy)-2,2-difluoro-3-methyl-6-<(4-methylphenyl)sulfinyl>cyclohexane | 156484-10-5

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: (1S,3R,6R,R_S)-1-(Benzyloxy)-2,2-difluoro-3-methyl-6-<(4-methylphenyl)sulfinyl>cyclohexane
• 英文别名: 1-[(R)-[(1R,2S,4R)-3,3-difluoro-4-methyl-2-phenylmethoxycyclohexyl]sulfinyl]-4-methylbenzene
• CAS: 156484-10-5
• 化学式: C₂₁H₂₄F₂O₂S
• 分子量: 378.483
• InChiKey: ZXHQZBLCICLVRJ-QIDUGFTHSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.7
• 重原子数：
  26
• 可旋转键数：
  5
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.43
• 拓扑面积：
  45.5
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  (1S,3R,6R,R_S)-1-(Benzyloxy)-2,2-difluoro-3-methyl-6-<(4-methylphenyl)sulfinyl>cyclohexane 在 2,4,6-三甲基吡啶 、 potassium carbonate 、 三氟乙酸酐 、 mercury dichloride 作用下， 生成 (4R)-2-(Benzyloxy)-3,3-difluoro-4-methyl-1-<(4-methylphenyl)thio>cyclohexene 、 (3S,5R)-3-(Benzyloxy)-4,4-difluoro-5-methyl-2-<(4-methylphenyl)thio>cyclohexene
  参考文献：
  名称：

  Synthesis of Enantiomerically Pure gem-Difluorocyclohexane Derivatives by Intramolecular Trapping of .alpha.,.alpha.-Difluoroalkyl Radicals

  摘要：

  gem-Difluorocyclohexanols 7 and 16 bearing, respectively, the arylsulfinyl and the arylthio substituent are obtained by radical-promoted cyclization from the corresponding omega-chlorodifluoroheptenols 6 and 9 in good yields. Intermediates 6 are made available by condensing the lithium derivative of chiral arylsulfinyl pentene 4 on ethyl chlorodifluoroacetate and by reducing the carbonyl with hydride-releasing agents. Elimination of the chiral auxiliary sulfinyl group and appropriate elaborations afford enantiomerically pure alpha-hydroxy-, alpha-hydroxy-Delta 3,4-, alpha,beta,gamma-trihydroxy-, and alpha-hydroxy-beta,gamma-epoxy-gem-difluorocyclohexane derivatives 19, 21, 22, and 23. Absolute and relative configurations as well as preferred conformations in solution are given. The degree of asymmetric induction during the radical-promoted cyclization is correlated with the relative configuration of substituted carbons in open-chain compounds.

  DOI：

  10.1021/jo00091a041
• 作为产物：
  描述：

  (-)-menthyl p-toluenesulfinate 在 ammonium hydroxide 、 sodium tetrahydroborate 、 偶氮二异丁腈 、 三正丁基氢锡 、 sodium hydride 、 lithium diisopropyl amide 作用下， 以 四氢呋喃 、 甲醇 、 N,N-二甲基甲酰胺 、 苯 为溶剂， 反应 7.25h， 生成 (1S,3R,6R,R_S)-1-(Benzyloxy)-2,2-difluoro-3-methyl-6-<(4-methylphenyl)sulfinyl>cyclohexane
  参考文献：
  名称：

  Synthesis of Enantiomerically Pure gem-Difluorocyclohexane Derivatives by Intramolecular Trapping of .alpha.,.alpha.-Difluoroalkyl Radicals

  摘要：

  gem-Difluorocyclohexanols 7 and 16 bearing, respectively, the arylsulfinyl and the arylthio substituent are obtained by radical-promoted cyclization from the corresponding omega-chlorodifluoroheptenols 6 and 9 in good yields. Intermediates 6 are made available by condensing the lithium derivative of chiral arylsulfinyl pentene 4 on ethyl chlorodifluoroacetate and by reducing the carbonyl with hydride-releasing agents. Elimination of the chiral auxiliary sulfinyl group and appropriate elaborations afford enantiomerically pure alpha-hydroxy-, alpha-hydroxy-Delta 3,4-, alpha,beta,gamma-trihydroxy-, and alpha-hydroxy-beta,gamma-epoxy-gem-difluorocyclohexane derivatives 19, 21, 22, and 23. Absolute and relative configurations as well as preferred conformations in solution are given. The degree of asymmetric induction during the radical-promoted cyclization is correlated with the relative configuration of substituted carbons in open-chain compounds.

  DOI：

  10.1021/jo00091a041