(2R,3S)-1-Chloro-1,1-difluoro-3-<(4-methylphenyl)thio>hept-6-en-2-ol | 136310-16-2

• 分子结构分类: 有机化合物 - 有机硫化合物 - 硫醚类
• 英文名称: (2R,3S)-1-Chloro-1,1-difluoro-3-<(4-methylphenyl)thio>hept-6-en-2-ol
• 英文别名: (2R,3S)-1-chloro-1,1-difluoro-3-<(4-methylphenyl)sulphenyl>hept-6-en-2-ol；(2R,3S)-1-chloro-1,1-difluoro-3-(4-methylphenyl)sulfanylhept-6-en-2-ol
• CAS: 136310-16-2
• 化学式: C₁₄H₁₇ClF₂OS
• 分子量: 306.804
• InChiKey: KPBVPALURJLZMY-QWHCGFSZSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.1
• 重原子数：
  19
• 可旋转键数：
  7
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.43
• 拓扑面积：
  45.5
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  (R)-(-)-2-苯基丙酸 、 (2R,3S)-1-Chloro-1,1-difluoro-3-<(4-methylphenyl)thio>hept-6-en-2-ol 在 4-二甲氨基吡啶 、 N,N'-二环己基碳二亚胺 作用下， 以 二氯甲烷 为溶剂， 反应 0.5h， 生成 (2R,3S)-1-Chloro-1,1-difluoro-3-<(4-methylphenyl)thio>hept-6-en-2-ol (-)-(R)-propionic ester
  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 、 三氟乙酸酐 、 sodium iodide 、 lithium diisopropyl amide 作用下， 以 四氢呋喃 、 甲醇 、 丙酮 为溶剂， 反应 0.42h， 生成 (2R,3S)-1-Chloro-1,1-difluoro-3-<(4-methylphenyl)thio>hept-6-en-2-ol
  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

文献信息

• Asymmetric synthesis of trisubstituted gem-difluorocyclohexanes by intramolecular trapping of difluoroalkyl radicals.
  作者：Alberto Arnone、Pierfrancesco Bravo、Fiorenza Viani、Giancarlo Cavicchio

  DOI：10.1016/s0957-4166(00)82161-8

  日期：1991.1

  gem-Difluorocyclohexanols 8 bearing a methyl and a p-tolyl-sulphinyl substituent have been synthesized in optically pure form by intramolecular trapping of difluoroalkyl radicals on terminal double bonds. The radical intermediates have been generated by the tributyltin hydride method from 1-chloro-1,1-difluoro-3-[(4-methylphenyl)sulphinyl]hept-6-en-2-ols (4), obtained by acylating (R)-p-tolyl-omega-pentenyl sulphoxide (1) with ethyl chlorodifluoroacetate (2) and by reducing the carbonyl of the beta-ketosulphoxide intermediate 3.