1,2-dideoxy-1,1-bis(methylsulfanyl)-3,4:6,7-di-O-isopropylidene-D-manno-hept-1-enitol | 197707-31-6

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 1,2-dideoxy-1,1-bis(methylsulfanyl)-3,4:6,7-di-O-isopropylidene-D-manno-hept-1-enitol
• 英文别名: (R)-[(4S,5R)-5-[2,2-bis(methylsulfanyl)ethenyl]-2,2-dimethyl-1,3-dioxolan-4-yl]-[(4R)-2,2-dimethyl-1,3-dioxolan-4-yl]methanol
• CAS: 197707-31-6
• 化学式: C₁₅H₂₆O₅S₂
• 分子量: 350.5
• InChiKey: CPQCJUMFEJHQCB-FPQZTECRSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.7
• 重原子数：
  22
• 可旋转键数：
  5
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.87
• 拓扑面积：
  108
• 氢给体数：
  1
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  1,2-dideoxy-1,1-bis(methylsulfanyl)-3,4:6,7-di-O-isopropylidene-D-manno-hept-1-enitol 在 mercury(II) perchlorate 、 二氧化硫 、 sodium formate 、 碳酸氢钠 作用下， 以 吡啶 、 N,N-二甲基甲酰胺 为溶剂， 反应 9.0h， 生成 (3aR,4R,7aR)-4-((R)-2,2-Dimethyl-[1,3]dioxolan-4-yl)-2,2-dimethyl-6-methylsulfanyl-7-trifluoromethyl-3a,7a-dihydro-4H-[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：

  双(甲硫代)三甲基硅甲烷 、 2,3:5,6-di-O-isopropylidene-α-D-mannofuranose 在 sodium hydride 、 正丁基锂 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 反应 2.0h， 以92%的产率得到1,2-dideoxy-1,1-bis(methylsulfanyl)-3,4:6,7-di-O-isopropylidene-D-manno-hept-1-enitol
  参考文献：
  名称：

  获得 3-Deoxy-d-manno-oct-2-ulosonic Acid (KDO) 和 3-Deoxy-d-arabino-hept-2-ulosonic Acid (DAH) 的一种新的短而有效的途径

  摘要：

  内酯 5 和 6 的有效合成，分别是 KDO 和 DAH 的已知中间体，已通过一条短而高效的路线实现。受保护的 D-甘露糖和 D-阿拉伯糖的同系化是通过与 2-锂硫-2-三甲基甲硅烷基二噻烷或相应的双（甲硫基）衍生物的彼得森反应进行的，然后在非常平稳的条件下环化得到的乙烯酮二硫缩醛。用碘进行氧化处理以高产率的三步顺序得到内酯 5 和 6。有趣的是，这种方法可以被认为是合成各种 2-脱氧糖内酯的通用方法。

  DOI：

  10.1055/s-2006-926375

文献信息

• A New Short and Efficient Route to 3-Deoxy-<scp>d</scp>-<i>manno</i>-oct-2-ulosonic Acid (KDO) and 3-Deoxy-<scp>d</scp>-<i>arabino</i>-hept-2-ulosonic Acid (DAH)
  作者：Richard Plantier-Royon、Charles Portella、Vincent Kikelj

  DOI：10.1055/s-2006-926375

  日期：——

  An efficient synthesis of lactones 5 and 6, known intermediates towards KDO and DAH, respectively, has been achieved by a short and highly efficient route. Homologation of protected D-mannose and D-arabinose was performed by a Peterson reaction with 2-lithio-2-trimethylsilyldithiane or the corresponding bis(methylsulfanyl) derivative, followed by the cyclization of the resulting ketene dithioacetal

  内酯 5 和 6 的有效合成，分别是 KDO 和 DAH 的已知中间体，已通过一条短而高效的路线实现。受保护的 D-甘露糖和 D-阿拉伯糖的同系化是通过与 2-锂硫-2-三甲基甲硅烷基二噻烷或相应的双（甲硫基）衍生物的彼得森反应进行的，然后在非常平稳的条件下环化得到的乙烯酮二硫缩醛。用碘进行氧化处理以高产率的三步顺序得到内酯 5 和 6。有趣的是，这种方法可以被认为是合成各种 2-脱氧糖内酯的通用方法。
• 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.