(1S,2S,4R,5S,7E)-5-<(4S,5R)-2,2-Dimethyl-5-vinyl-1,3-dioxolan-4-yl>-2-(methoxymethoxy)-4,11,11-trimethylbicyclo<6.2.1>undec-7-en-3-one | 171419-51-5

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (1S,2S,4R,5S,7E)-5-<(4S,5R)-2,2-Dimethyl-5-vinyl-1,3-dioxolan-4-yl>-2-(methoxymethoxy)-4,11,11-trimethylbicyclo<6.2.1>undec-7-en-3-one
• CAS: 171419-51-5
• 化学式: C₂₃H₃₆O₅
• 分子量: 392.536
• InChiKey: QNKOMOUMFBZYGN-JMXJNGNBSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.27
• 重原子数：
  28.0
• 可旋转键数：
  5.0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.78
• 拓扑面积：
  53.99
• 氢给体数：
  0.0
• 氢受体数：
  5.0

反应信息

• 作为反应物：
  描述：

  (1S,2S,4R,5S,7E)-5-<(4S,5R)-2,2-Dimethyl-5-vinyl-1,3-dioxolan-4-yl>-2-(methoxymethoxy)-4,11,11-trimethylbicyclo<6.2.1>undec-7-en-3-one 在 四氧化锇 、 甲基磺酰胺 、 四丁基碘化铵 、 二异丁基氢化铝 、 二正丁基氧化锡 、 potassium carbonate 、 potassium hexacyanoferrate(III) 作用下， 以 水 、 异丙醇 、 甲苯 为溶剂， 反应 15.0h， 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：

  替格瑞洛杂质128 在 18-冠醚-6 、 叔丁基锂 、 sodium hexamethyldisilazane 、 双(三甲基硅烷基)氨基钾 作用下， 以 四氢呋喃 、 正戊烷 为溶剂， 反应 3.75h， 生成 (1S,2S,4R,5S,7E)-5-<(4S,5R)-2,2-Dimethyl-5-vinyl-1,3-dioxolan-4-yl>-2-(methoxymethoxy)-4,11,11-trimethylbicyclo<6.2.1>undec-7-en-3-one
  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