2,3-O-isopropylidene-5-C-methyl-β-D-talo-hexofuranose | 127589-00-8

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 2,3-O-isopropylidene-5-C-methyl-β-D-talo-hexofuranose
• 英文别名: 2,3-O-isopropylidene-5-C-methyl-α-D-talo-hexofuranose；2,3-O-isopropylidene-5-C-methyl-αβ-D-talo-hexofuranose
• CAS: 127589-00-8；127589-06-4；139391-30-3；139391-50-7
• 化学式: C₁₀H₁₈O₆
• 分子量: 234.249
• InChiKey: SQCLYCNQFACDOP-WONAEBKGSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -1.03
• 重原子数：
  16.0
• 可旋转键数：
  2.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  88.38
• 氢给体数：
  3.0
• 氢受体数：
  6.0

反应信息

• 作为反应物：
  描述：

  2,3-O-isopropylidene-5-C-methyl-β-D-talo-hexofuranose 在 硫酸 作用下， 以 水 为溶剂， 反应 2.0h， 生成 5-C-methyl-α-D-talo-hexose 、 5-C-methyl-β-D-talo-hexose
  参考文献：
  名称：

  Total, asymmetric synthesis of hexoses and azasugars branched at C(5).

  摘要：

  The Diels-Alder adduct (-)-5 (a "naked sugar") of furan to 1-cyanovinyl (1R')-camphanate was converted into (+)-(1R,5S,6S,7S)-6-exo,7-exo-(isopropylidenedioxy)-2,8-dioxabicylo[3.2.1]octan-3-one and into (+)-(1R,5S,6S,7S)-7-endo-(benzyloxy)-6-exo-{[(t-butyl)dimethylsilyl]oxy}-2,8-dioxabicyclo[3.2.1]-octan-3-one ((+)-17). Double methylation at C(4) gave the corresponding 5-deoxy-5-C-dimethyl furanurono-6,1-lactones (+)-42 and (+)-19, respectively. Stereoselective and successive methylation and benzyloxymethylation of (+)-(1R,5S,6S,7S)-6-exo,-7-exo-(isopropylidenedioxy)2,8-dioxabicyclo[3.2.1]octan-3-one gave (+)-(1R,4R,5S,6S,7S)4-exo-[(benzyloxy)methyl]-6-exo,7-exo-(isopropylidenedioxy)-4-endo-methyl-2,8-dioxabicyclo[3.2.1]octan-3-one ((+)-9). Highly stereoselective oxydative decarboxylation of lactones (+)-9 and (+)-19 led to 5-C-methyl-alpha-beta-D-talo-hexose ((-)-1) and to 6-deoxy-5-C-methyl-alpha-beta-L-arabino-hexose ((-)-2), respectively. Transformation of lactones (+)-9 and (+)-42 into the corresponding acyl azides and their Curtius rearrangements led to (5-ammonio-1,5-N-anhydro-5-deoxy-5-C-methyl-alpha-beta-D-talo-hexitol)-1-sulfonate ((+)-3) and to (5-ammonio-1,5-N-anhydro-5,6-dideoxy-5-C-methyl-alpha-beta-L-ribo-hexitol)1-sulfonate ((+)-4), respectively.

  DOI：

  10.1016/s0040-4020(01)91030-0
• 作为产物：
  描述：

  (1S,2S,6S,7R,10R)-4,4,10-Trimethyl-3,5,8,11-tetraoxa-tricyclo[5.3.1.0^2,6]undecan-9-one 在 palladium on activated charcoal 吡啶 、 甲醇 、 disodium hydrogenphosphate 、 三氟过氧乙酸 、 氢气 、 potassium carbonate 、 lithium hexamethyldisilazane 作用下， 以 四氢呋喃 、 甲醇 、 二氯甲烷 、 水 为溶剂， -65.0~20.0 ℃ 、101.33 kPa 条件下， 反应 29.92h， 生成 2,3-O-isopropylidene-5-C-methyl-β-D-talo-hexofuranose
  参考文献：
  名称：

  Total, asymmetric synthesis of hexoses and azasugars branched at C(5).

  摘要：

  The Diels-Alder adduct (-)-5 (a "naked sugar") of furan to 1-cyanovinyl (1R')-camphanate was converted into (+)-(1R,5S,6S,7S)-6-exo,7-exo-(isopropylidenedioxy)-2,8-dioxabicylo[3.2.1]octan-3-one and into (+)-(1R,5S,6S,7S)-7-endo-(benzyloxy)-6-exo-{[(t-butyl)dimethylsilyl]oxy}-2,8-dioxabicyclo[3.2.1]-octan-3-one ((+)-17). Double methylation at C(4) gave the corresponding 5-deoxy-5-C-dimethyl furanurono-6,1-lactones (+)-42 and (+)-19, respectively. Stereoselective and successive methylation and benzyloxymethylation of (+)-(1R,5S,6S,7S)-6-exo,-7-exo-(isopropylidenedioxy)2,8-dioxabicyclo[3.2.1]octan-3-one gave (+)-(1R,4R,5S,6S,7S)4-exo-[(benzyloxy)methyl]-6-exo,7-exo-(isopropylidenedioxy)-4-endo-methyl-2,8-dioxabicyclo[3.2.1]octan-3-one ((+)-9). Highly stereoselective oxydative decarboxylation of lactones (+)-9 and (+)-19 led to 5-C-methyl-alpha-beta-D-talo-hexose ((-)-1) and to 6-deoxy-5-C-methyl-alpha-beta-L-arabino-hexose ((-)-2), respectively. Transformation of lactones (+)-9 and (+)-42 into the corresponding acyl azides and their Curtius rearrangements led to (5-ammonio-1,5-N-anhydro-5-deoxy-5-C-methyl-alpha-beta-D-talo-hexitol)-1-sulfonate ((+)-3) and to (5-ammonio-1,5-N-anhydro-5,6-dideoxy-5-C-methyl-alpha-beta-L-ribo-hexitol)1-sulfonate ((+)-4), respectively.

  DOI：

  10.1016/s0040-4020(01)91030-0