(1S,2S,5S,6R,7R,8R,9S)-9-<(1S,2R)-2-Hydroxy-1-isopropoxy-3-butenyl>-6-(methoxymethoxy)-8,12,12-trimethyl-11-oxatricyclo<5.3.1.1^2,5>dodecane-2,7-diol | 171419-53-7

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 异戊烯醇脂质
• 英文名称: (1S,2S,5S,6R,7R,8R,9S)-9-<(1S,2R)-2-Hydroxy-1-isopropoxy-3-butenyl>-6-(methoxymethoxy)-8,12,12-trimethyl-11-oxatricyclo<5.3.1.1^2,5>dodecane-2,7-diol
• CAS: 171419-53-7
• 化学式: C₂₃H₄₀O₇
• 分子量: 428.566
• InChiKey: NPTDWXQKTBSRDD-FYWZJNMFSA-N

物化性质

• 沸点：
  535.2±50.0 °C(predicted)
• 密度：
  1.16±0.1 g/cm3(Temp: 20 °C; Press: 760 Torr)(predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.23
• 重原子数：
  30.0
• 可旋转键数：
  8.0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.91
• 拓扑面积：
  97.61
• 氢给体数：
  3.0
• 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-<(1S,2R)-2-Hydroxy-1-isopropoxy-3-butenyl>-6-(methoxymethoxy)-8,12,12-trimethyl-11-oxatricyclo<5.3.1.1^2,5>dodecane-2,7-diol 在 4-二甲氨基吡啶 、 四丁基碘化铵 、 二正丁基氧化锡 、 三乙胺 作用下， 以 二氯甲烷 为溶剂， 反应 25.0h， 生成 [(1S,2R)-1-[(1S,2S,5S,6R,7R,8R,9S)-1-[(2-bromophenyl)methoxy]-2-hydroxy-6-(methoxymethoxy)-8,12,12-trimethyl-11-oxatricyclo[5.3.1.12,5]dodecan-9-yl]-1-propan-2-yloxybut-3-en-2-yl] 4-nitrobenzoate
  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,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 二异丁基氢化铝 作用下， 以 甲苯 为溶剂， 反应 3.5h， 以83%的产率得到(1S,2S,5S,6R,7R,8R,9S)-9-<(1S,2R)-2-Hydroxy-1-isopropoxy-3-butenyl>-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