(2S,3S,4S,5R)-3,5;4,6-Bis(isopropylidenedioxy)-4-methyl-1-(phenylthio)-2-hexanol | 154547-80-5

• 分子结构分类: 有机化合物 - 有机硫化合物 - 硫醚类
• 英文名称: (2S,3S,4S,5R)-3,5;4,6-Bis(isopropylidenedioxy)-4-methyl-1-(phenylthio)-2-hexanol
• 英文别名: (1S)-1-[(4S,4aS,8aR)-2,2,4a,6,6-pentamethyl-8,8a-dihydro-4H-[1,3]dioxino[5,4-d][1,3]dioxin-4-yl]-2-phenylsulfanylethanol
• CAS: 154547-80-5
• 化学式: C₁₉H₂₈O₅S
• 分子量: 368.494
• InChiKey: JXKOAMJRNUKWGB-JEWRLFTDSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.6
• 重原子数：
  25
• 可旋转键数：
  4
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.68
• 拓扑面积：
  82.4
• 氢给体数：
  1
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  (2S,3S,4S,5R)-3,5;4,6-Bis(isopropylidenedioxy)-4-methyl-1-(phenylthio)-2-hexanol 在 间氯过氧苯甲酸 作用下， 以 二氯甲烷 为溶剂， 反应 1.5h， 以95%的产率得到(2S,3S,4S,5R)-3,5;4,6-Bis(isopropylidenedioxy)-4-methyl-1-(phenylsulfinyl)-2-hexanol
  参考文献：
  名称：

  Enantioselective Synthesis of Carbohydrate Precursors via 1,2:2,3-Bis-Epoxide Intermediates

  摘要：

  Bis-epoxidation of the DPS-substituted allenylcarbinyl acetates 9, 13, 19, 22, and 30 afforded the enones 10, 36, 20, 23, and 31, respectively, in 80-90 % yield with excellent stereoselectivity. Treatment with DBU effected C to O DPS transfer leading to the methyl-branched hexose precursors, enones 11, 37, 21, and 24. The higher homologue 33 gave the branched 7-deoxyheptose precursor 33. Reduction of enones 11, 37, and 33 with NaBH4-CeCl3 yielded the alpha-(S) alcohols 12, 38, and 35 in high yield. Alcohol 38 was converted to the 1-deoxy-4-methylpyranose tetraacetate 48 by epoxidation, base treatment, desilylation, and acetylation. An acyclic analogue of 48, acetonide 53, could be prepared from epoxide 39 by treatment with PhSH and NaOH, followed by silyl ether cleavage, acetonide formation, and Pummerer rearrangement-reduction. On the other hand, hydroxylation of alcohol 38 with OsO4-NMO led to the selectively protected branched hexitol 59, with high diastereoselectivity. The allylic alcohol benzoate 63 was likewise converted to diol 64.

  DOI：

  10.1021/jo00085a038
• 作为产物：
  描述：

  Acetic acid (1R,2S)-1-(tert-butyl-dimethyl-silanyloxymethyl)-4-(tert-butyl-diphenyl-silanyl)-2-hydroxy-2-methyl-3-oxo-pent-4-enyl ester 在 叔丁基过氧化氢 、 sodium hydroxide 、 sodium tetrahydroborate 、 cerium(III) chloride 、 bis(acetylacetonate)oxovanadium 、 四丁基氟化铵 、 对甲苯磺酸 、 1,8-二氮杂双环[5.4.0]十一碳-7-烯 作用下， 以 四氢呋喃 、 1,4-二氧六环 、 甲醇 、 异辛烷 、 二氯甲烷 、 甲苯 为溶剂， 反应 28.0h， 生成 (2S,3S,4S,5R)-3,5;4,6-Bis(isopropylidenedioxy)-4-methyl-1-(phenylthio)-2-hexanol
  参考文献：
  名称：

  Enantioselective Synthesis of Carbohydrate Precursors via 1,2:2,3-Bis-Epoxide Intermediates

  摘要：

  Bis-epoxidation of the DPS-substituted allenylcarbinyl acetates 9, 13, 19, 22, and 30 afforded the enones 10, 36, 20, 23, and 31, respectively, in 80-90 % yield with excellent stereoselectivity. Treatment with DBU effected C to O DPS transfer leading to the methyl-branched hexose precursors, enones 11, 37, 21, and 24. The higher homologue 33 gave the branched 7-deoxyheptose precursor 33. Reduction of enones 11, 37, and 33 with NaBH4-CeCl3 yielded the alpha-(S) alcohols 12, 38, and 35 in high yield. Alcohol 38 was converted to the 1-deoxy-4-methylpyranose tetraacetate 48 by epoxidation, base treatment, desilylation, and acetylation. An acyclic analogue of 48, acetonide 53, could be prepared from epoxide 39 by treatment with PhSH and NaOH, followed by silyl ether cleavage, acetonide formation, and Pummerer rearrangement-reduction. On the other hand, hydroxylation of alcohol 38 with OsO4-NMO led to the selectively protected branched hexitol 59, with high diastereoselectivity. The allylic alcohol benzoate 63 was likewise converted to diol 64.

  DOI：

  10.1021/jo00085a038