(methyl 5-deoxy-5,5-dimethyl-2,3-O-isopropylidene-β-D,L-ribo-hexofuranosid)uronamide | 139391-45-0

• 分子结构分类: 有机化合物 - 有机酸及其衍生物
• 英文名称: (methyl 5-deoxy-5,5-dimethyl-2,3-O-isopropylidene-β-D,L-ribo-hexofuranosid)uronamide
• CAS: 139391-45-0；139391-71-2
• 化学式: C₁₂H₂₁NO₅
• 分子量: 259.302
• InChiKey: LPLKEOVNGYSUTG-XAVMHZPKSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.39
• 重原子数：
  18.0
• 可旋转键数：
  3.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.92
• 拓扑面积：
  80.01
• 氢给体数：
  1.0
• 氢受体数：
  5.0

反应信息

• 作为反应物：
  描述：

  (methyl 5-deoxy-5,5-dimethyl-2,3-O-isopropylidene-β-D,L-ribo-hexofuranosid)uronamide 在 [双(三氟乙酰氧基)碘]苯 作用下， 以 水 、 乙腈 为溶剂， 反应 5.0h， 以41%的产率得到methyl 5-amino-5,6-dideoxy-2,3-O-isopropylidene-5-C-methyl-β-L-ribo-hexofuranoside
  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：

  rac-(ethyl carbonic) 2-((3aR,4R,6R,6aR)-6-methoxy-2,2-dimethyltetrahydrofuro[3,4-d][1,3]dioxol-4-yl)-2-methylpropanoic anhydride 在 氨 作用下， 以 二氯甲烷 为溶剂， 以92%的产率得到(methyl 5-deoxy-5,5-dimethyl-2,3-O-isopropylidene-β-D,L-ribo-hexofuranosid)uronamide
  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