(1S,2S,5S,6R,7R,8R,9S)-9-<(4S,5R)-2,2-Dimethyl-5-vinyl-1,3-dioxolan-4-yl>-6-(methoxymethoxy)-8,12,12-trimethyl-11-oxatricyclo<5.3.1.1^2,5>dodecane-2,7-diol | 171419-52-6

• 分子结构分类: 有机化合物 - 脂质和类脂质分子
• 英文名称: (1S,2S,5S,6R,7R,8R,9S)-9-<(4S,5R)-2,2-Dimethyl-5-vinyl-1,3-dioxolan-4-yl>-6-(methoxymethoxy)-8,12,12-trimethyl-11-oxatricyclo<5.3.1.1^2,5>dodecane-2,7-diol
• 英文别名: (1S,2S,5S,6R,7R,8R,9S)-9-[(4S,5R)-5-ethenyl-2,2-dimethyl-1,3-dioxolan-4-yl]-6-(methoxymethoxy)-8,12,12-trimethyl-11-oxatricyclo[5.3.1.12,5]dodecane-2,7-diol
• CAS: 171419-52-6
• 化学式: C₂₃H₃₈O₇
• 分子量: 426.551
• InChiKey: FORQIJOFTYEYLP-WLVFSEHSSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.59
• 重原子数：
  30.0
• 可旋转键数：
  5.0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.91
• 拓扑面积：
  86.61
• 氢给体数：
  2.0
• 氢受体数：
  7.0

反应信息

• 作为反应物：
  描述：

  (1S,2S,5S,6R,7R,8R,9S)-9-<(4S,5R)-2,2-Dimethyl-5-vinyl-1,3-dioxolan-4-yl>-6-(methoxymethoxy)-8,12,12-trimethyl-11-oxatricyclo<5.3.1.1^2,5>dodecane-2,7-diol 在 四丁基碘化铵 、 二异丁基氢化铝 、 二正丁基氧化锡 作用下， 以 甲苯 为溶剂， 反应 12.5h， 生成 (1S,2S,5S,6R,7R,8R,9S)-1-[(2-bromophenyl)methoxy]-9-[(1S,2R)-2-hydroxy-1-propan-2-yloxybut-3-enyl]-6-(methoxymethoxy)-8,12,12-trimethyl-11-oxatricyclo[5.3.1.12,5]dodecan-2-ol
  参考文献：
  名称：

  Evaluation of D-Ribose as an Enantiopure Building Block for Construction of the C-Ring of Taxol and Its Congeners

  摘要：

  The enantiomerically pure Z vinyl iodide 20 is shown to be readily available from D-ribose via a sequence involving zinc-promoted reductive unmasking of an aldehyde and homologation with (iodomethylene)triphenylphosphorane. The vinyl anion produced by halogen-metal exchange adds from the endo direction to an enantiopure ketone prepared from D-camphor. The resulting carbinol undergoes anionic oxy-Cope rearrangement and C-methylation with complete stereocontrol to set the appropriate C-3 stereochemistry of taxol. Dihydroxylation of this intermediate brings about facile transannular hemiketalization. DIBAL-H reduction of this intermediate does not affect the hemiketal, but does reduce the acetonide regiospecifically. An unusual transannular hydride shift occurs during subsequent heating with dibutyltin oxide, as confirmed by X-ray crystallography. When transannular hemiketalization is skirted, hydroboration-oxidation of the side chain leads to an acetaldehyde which is notably prone to beta-elimination. Treatment with potassium carbonate in methanol does eventuate in ring closure via an aldol addition reaction, but only after methanol has been added in Michael fashion to the alpha,beta-unsaturated aldehyde.

  DOI：

  10.1021/jo00129a026
• 作为产物：
  描述：

  (1S,2S,3R,4S)-2-<(Z)-2-<(4S,5R)-2,2-Dimethyl-5-vinyl-1,3-dioxolan-4-yl>vinyl>-3-(methoxymethoxy)-7,7-dimethyl-1-vinyl-2-norbornanol 在 吡啶 、 咪唑 、 四氧化锇 、 18-冠醚-6 、 双(三甲基硅烷基)氨基钾 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 42.33h， 生成 (1S,2S,5S,6R,7R,8R,9S)-9-<(4S,5R)-2,2-Dimethyl-5-vinyl-1,3-dioxolan-4-yl>-6-(methoxymethoxy)-8,12,12-trimethyl-11-oxatricyclo<5.3.1.1^2,5>dodecane-2,7-diol
  参考文献：
  名称：

  Evaluation of D-Ribose as an Enantiopure Building Block for Construction of the C-Ring of Taxol and Its Congeners

  摘要：

  The enantiomerically pure Z vinyl iodide 20 is shown to be readily available from D-ribose via a sequence involving zinc-promoted reductive unmasking of an aldehyde and homologation with (iodomethylene)triphenylphosphorane. The vinyl anion produced by halogen-metal exchange adds from the endo direction to an enantiopure ketone prepared from D-camphor. The resulting carbinol undergoes anionic oxy-Cope rearrangement and C-methylation with complete stereocontrol to set the appropriate C-3 stereochemistry of taxol. Dihydroxylation of this intermediate brings about facile transannular hemiketalization. DIBAL-H reduction of this intermediate does not affect the hemiketal, but does reduce the acetonide regiospecifically. An unusual transannular hydride shift occurs during subsequent heating with dibutyltin oxide, as confirmed by X-ray crystallography. When transannular hemiketalization is skirted, hydroboration-oxidation of the side chain leads to an acetaldehyde which is notably prone to beta-elimination. Treatment with potassium carbonate in methanol does eventuate in ring closure via an aldol addition reaction, but only after methanol has been added in Michael fashion to the alpha,beta-unsaturated aldehyde.

  DOI：

  10.1021/jo00129a026