(3aR,4R,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-one | 197707-36-1

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 二氧吡喃
• 英文名称: (3aR,4R,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-one
• 英文别名: (3aR,4R,7R,7aR)-4-[(4R)-2,2-dimethyl-1,3-dioxolan-4-yl]-2,2-dimethyl-7-(trifluoromethyl)-3a,4,7,7a-tetrahydro-[1,3]dioxolo[4,5-c]pyran-6-one
• CAS: 197707-36-1
• 化学式: C₁₄H₁₉F₃O₆
• 分子量: 340.296
• InChiKey: YYBWSJZBKNCVBD-IGORNWKESA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.6
• 重原子数：
  23
• 可旋转键数：
  1
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.93
• 拓扑面积：
  63.2
• 氢给体数：
  0
• 氢受体数：
  9

反应信息

• 作为反应物：
  描述：

  (3aR,4R,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-one 在 silica gel 作用下， 生成 (3aR,4R,7S,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-one
  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 、 lindane 、 二氧化硫 、 sodium formate 、 sodium hydride 、 碳酸氢钠 、 calcium carbonate 作用下， 以 四氢呋喃 、 吡啶 、 水 、 N,N-二甲基甲酰胺 、 丙酮 为溶剂， 反应 10.0h， 生成 (3aR,4R,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-one
  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

文献信息

• Radical Trifluoromethylation of a <scp>d</scp>-Mannose Derived Ketene Dithioacetal. Synthesis of 2-<i>C</i>-Trifluoromethyl Derivatives of <scp>d</scp>-<i>glycero</i>-<scp>d</scp>-<i>galacto</i>- and <scp>d</scp>-<i>glycero</i>-<scp>d</scp>-<i>talo</i>-Heptopyranose
  作者：G. Foulard、T. Brigaud、C. Portella

  DOI：10.1021/jo971187o

  日期：1997.12.1

  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.