(R)-[(4R)-2,2-dimethyl-1,3-dioxolan-4-yl]-[(4S,5R)-2,2-dimethyl-5-[(2S)-1,1,1-trifluoro-3,3-bis(methylsulfanyl)propan-2-yl]-1,3-dioxolan-4-yl]methanol | 197707-35-0

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (R)-[(4R)-2,2-dimethyl-1,3-dioxolan-4-yl]-[(4S,5R)-2,2-dimethyl-5-[(2S)-1,1,1-trifluoro-3,3-bis(methylsulfanyl)propan-2-yl]-1,3-dioxolan-4-yl]methanol
• CAS: 197707-35-0
• 化学式: C₁₆H₂₇F₃O₅S₂
• 分子量: 420.515
• InChiKey: XMXPWWSWOJFRQT-OOCWMUITSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3
• 重原子数：
  26
• 可旋转键数：
  6
• 环数：
  2.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  108
• 氢给体数：
  1
• 氢受体数：
  10

反应信息

• 作为反应物：
  描述：

  (R)-[(4R)-2,2-dimethyl-1,3-dioxolan-4-yl]-[(4S,5R)-2,2-dimethyl-5-[(2S)-1,1,1-trifluoro-3,3-bis(methylsulfanyl)propan-2-yl]-1,3-dioxolan-4-yl]methanol 在 碘 、 calcium carbonate 作用下， 以 四氢呋喃 、 水 为溶剂， 反应 1.5h， 生成 (3aR,4R,6R,7R,7aR)-4-((R)-2,2-Dimethyl-[1,3]dioxolan-4-yl)-2,2-dimethyl-7-trifluoromethyl-tetrahydro-[1,3]dioxolo[4,5-c]pyran-6-ol 、 (3aR,4R,6S,7R,7aR)-4-((R)-2,2-Dimethyl-[1,3]dioxolan-4-yl)-2,2-dimethyl-7-trifluoromethyl-tetrahydro-[1,3]dioxolo[4,5-c]pyran-6-ol 、 (3aR,4R,6S,7S,7aR)-4-((R)-2,2-Dimethyl-[1,3]dioxolan-4-yl)-2,2-dimethyl-6-methylsulfanyl-7-trifluoromethyl-tetrahydro-[1,3]dioxolo[4,5-c]pyran 、 (3aR,4R,6R,7S,7aR)-4-((R)-2,2-Dimethyl-[1,3]dioxolan-4-yl)-2,2-dimethyl-6-methylsulfanyl-7-trifluoromethyl-tetrahydro-[1,3]dioxolo[4,5-c]pyran
  参考文献：
  名称：

  Radical Trifluoromethylation of a d-Mannose Derived Ketene Dithioacetal. Synthesis of 2-C-Trifluoromethyl Derivatives of d-glycero-d-galacto- and d-glycero-d-talo-Heptopyranose

  摘要：

  Diacetone D-mannose was converted into ketene dithioacetals 3 by a Peterson reaction with 2-lithio-2-(trimethylsilyl)-1,3-dithiane or lithiobis(methylsulfanyl)(trimethylsilyl)methane. Radical addition of trifluoromethyl bromide (iodide) induced by electron transfer (from sulfoxylate radical anion) led selectively to a dithioketalized 2-deoxy-2-C-(trifluoromethyl)-D-glycero-D-galacto-heptopyranolactone (5a) or to the corresponding dithioketalized open sugar 9, mainly according to the alkylsulfanyl group. Reaction conditions were found for complete or partial dethioketalization of these intermediates. A diisopropylidene-protected 2-deoxy-2-C-(trifluoromethyl)-D-glycero-D-talo-heptopyranolactone (12) was obtained from 5a, with concomitant epimerization of C-2. Compound 9 was converted into either the corresponding sugar 14 or its methyl thioglycoside 13. Most of these reactions gave preparative yields, and the overall sequence constitutes a three-step synthesis of 2-deoxy-2-C-(trifluoromethyl)-D-glycero-D-galacto-heptose or D-talo-heptose derivatives.

  DOI：

  10.1021/jo971187o
• 作为产物：
  描述：

  2,3,5,6-di-O-isopropylidene-D-mannofuranose 在 正丁基锂 、 二氧化硫 、 sodium formate 、 sodium hydride 、 碳酸氢钠 作用下， 以 吡啶 、 N,N-二甲基甲酰胺 为溶剂， 反应 10.0h， 生成 (R)-[(4R)-2,2-dimethyl-1,3-dioxolan-4-yl]-[(4S,5R)-2,2-dimethyl-5-[(2S)-1,1,1-trifluoro-3,3-bis(methylsulfanyl)propan-2-yl]-1,3-dioxolan-4-yl]methanol
  参考文献：
  名称：

  Radical Trifluoromethylation of a d-Mannose Derived Ketene Dithioacetal. Synthesis of 2-C-Trifluoromethyl Derivatives of d-glycero-d-galacto- and d-glycero-d-talo-Heptopyranose

  摘要：

  Diacetone D-mannose was converted into ketene dithioacetals 3 by a Peterson reaction with 2-lithio-2-(trimethylsilyl)-1,3-dithiane or lithiobis(methylsulfanyl)(trimethylsilyl)methane. Radical addition of trifluoromethyl bromide (iodide) induced by electron transfer (from sulfoxylate radical anion) led selectively to a dithioketalized 2-deoxy-2-C-(trifluoromethyl)-D-glycero-D-galacto-heptopyranolactone (5a) or to the corresponding dithioketalized open sugar 9, mainly according to the alkylsulfanyl group. Reaction conditions were found for complete or partial dethioketalization of these intermediates. A diisopropylidene-protected 2-deoxy-2-C-(trifluoromethyl)-D-glycero-D-talo-heptopyranolactone (12) was obtained from 5a, with concomitant epimerization of C-2. Compound 9 was converted into either the corresponding sugar 14 or its methyl thioglycoside 13. Most of these reactions gave preparative yields, and the overall sequence constitutes a three-step synthesis of 2-deoxy-2-C-(trifluoromethyl)-D-glycero-D-galacto-heptose or D-talo-heptose derivatives.

  DOI：

  10.1021/jo971187o