2-[(4R,5S)-5-[(1S,2S,4S,5R,7R,8S)-2-[tert-butyl(dimethyl)silyl]oxy-1-hydroxy-7-(methoxymethoxy)-5,11,11-trimethyl-6-oxo-4-bicyclo[6.2.1]undecanyl]-2,2-dimethyl-1,3-dioxolan-4-yl]acetaldehyde | 171419-57-1

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 2-[(4R,5S)-5-[(1S,2S,4S,5R,7R,8S)-2-[tert-butyl(dimethyl)silyl]oxy-1-hydroxy-7-(methoxymethoxy)-5,11,11-trimethyl-6-oxo-4-bicyclo[6.2.1]undecanyl]-2,2-dimethyl-1,3-dioxolan-4-yl]acetaldehyde
• CAS: 171419-57-1
• 化学式: C₂₉H₅₂O₈Si
• 分子量: 556.813
• InChiKey: SDCWOTXLEZIPAI-IPDNWURVSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.87
• 重原子数：
  38
• 可旋转键数：
  9
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.93
• 拓扑面积：
  101
• 氢给体数：
  1
• 氢受体数：
  8

反应信息

• 作为反应物：
  描述：

  2-[(4R,5S)-5-[(1S,2S,4S,5R,7R,8S)-2-[tert-butyl(dimethyl)silyl]oxy-1-hydroxy-7-(methoxymethoxy)-5,11,11-trimethyl-6-oxo-4-bicyclo[6.2.1]undecanyl]-2,2-dimethyl-1,3-dioxolan-4-yl]acetaldehyde 在 silica gel 作用下， 生成 (1S,2'E,2S,3'S,4S,5R,7R,8S)-2-(tert-Butyldimethylsiloxy)-4-(3-formyl-1-hydroxy-2-propenyl)-1-hydroxy-7-(methoxymethoxy)-5,11,11-trimethyloxobicyclo<6.2.1>undecan-6-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
• 作为产物：
  描述：

  (1S,2R,4R,5S,7S,8S)-7-[tert-butyl(dimethyl)silyl]oxy-5-[(4S,5R)-5-ethenyl-2,2-dimethyl-1,3-dioxolan-4-yl]-8-hydroxy-2-(methoxymethoxy)-4,11,11-trimethylbicyclo[6.2.1]undecan-3-one 在 吡啶 、 sodium hydroxide 、 2,3-二甲基-2-丁烯 、 硼烷四氢呋喃络合物 、 双氧水 、 戴斯-马丁氧化剂 作用下， 以 二氯甲烷 为溶剂， 反应 4.0h， 生成 2-[(4R,5S)-5-[(1S,2S,4S,5R,7R,8S)-2-[tert-butyl(dimethyl)silyl]oxy-1-hydroxy-7-(methoxymethoxy)-5,11,11-trimethyl-6-oxo-4-bicyclo[6.2.1]undecanyl]-2,2-dimethyl-1,3-dioxolan-4-yl]acetaldehyde
  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