[(2S,4R,5S)-5-[(1S,2S,4S,5S,7R,8S)-2-(tert-Butyl-dimethyl-silanyloxy)-1-hydroxy-7-methoxymethoxy-5,11,11-trimethyl-6-oxo-bicyclo[6.2.1]undec-4-yl]-2-(4-methoxy-phenyl)-5-(2-trimethylsilanyl-ethoxymethoxy)-[1,3]dioxan-4-yl]-acetaldehyde | 217820-22-9

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯酚醚
• 英文名称: [(2S,4R,5S)-5-[(1S,2S,4S,5S,7R,8S)-2-(tert-Butyl-dimethyl-silanyloxy)-1-hydroxy-7-methoxymethoxy-5,11,11-trimethyl-6-oxo-bicyclo[6.2.1]undec-4-yl]-2-(4-methoxy-phenyl)-5-(2-trimethylsilanyl-ethoxymethoxy)-[1,3]dioxan-4-yl]-acetaldehyde
• 英文别名: 2-[(2S,4R,5S)-5-[(1S,2S,4S,5S,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-(4-methoxyphenyl)-5-(2-trimethylsilylethoxymethoxy)-1,3-dioxan-4-yl]acetaldehyde
• CAS: 217820-22-9
• 化学式: C₄₁H₇₀O₁₁Si₂
• 分子量: 795.171
• InChiKey: CDFFZSCFKCKHPY-FYXSPGOQSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7.54
• 重原子数：
  54
• 可旋转键数：
  17
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.8
• 拓扑面积：
  128
• 氢给体数：
  1
• 氢受体数：
  11

反应信息

• 作为反应物：
  描述：

  [(2S,4R,5S)-5-[(1S,2S,4S,5S,7R,8S)-2-(tert-Butyl-dimethyl-silanyloxy)-1-hydroxy-7-methoxymethoxy-5,11,11-trimethyl-6-oxo-bicyclo[6.2.1]undec-4-yl]-2-(4-methoxy-phenyl)-5-(2-trimethylsilanyl-ethoxymethoxy)-[1,3]dioxan-4-yl]-acetaldehyde 在 sodium hydroxide 作用下， 以 四氢呋喃 、 甲醇 为溶剂， 生成 (1S,2R,4R,5R,8S,9S,11S,12S)-11-(tert-Butyl-dimethyl-silanyloxy)-5,12-dihydroxy-8-hydroxymethyl-2-methoxymethoxy-4,15,15-trimethyl-8-(2-trimethylsilanyl-ethoxymethoxy)-tricyclo[10.2.1.0^4,9]pentadec-6-en-3-one 、 (1S,2S,4S,5S,8S,10R,12R,13R,15R,16S)-2-[tert-butyl(dimethyl)silyl]oxy-1,12-dihydroxy-15-(methoxymethoxy)-8-(4-methoxyphenyl)-13,19,19-trimethyl-5-(2-trimethylsilylethoxymethoxy)-7,9-dioxatetracyclo[14.2.1.04,13.05,10]nonadecan-14-one
  参考文献：
  名称：

  Stereochemical Models for the Enantiocontrolled Construction of Fully Functionalized C Rings via Intramolecular Aldolization in Advanced Precursors to Paclitaxel

  摘要：

  Six transition-state models for intramolecular aldol C-ring annulation in suitably substituted bicyclo-[6.2.1]undecanones have been defined. The first consideration is the inherent conformational flexibility of the nine-membered ketonic ring which does not limit effective deprotonation to a single C-8 epimer. When the oxygen substituents at C-4 and C-5 are not covalently linked, the configuration at C-5 defines the stereochemical course of the ring closure, with only the beta series being amenable to the proper elaboration of paclitaxel. When C-4 and C-5 are incorporated into a 1,3-dioxane ring instead, the principal stereocontrol element is translocated into the aryl-substituted carbon of the cyclic acetal. To the extent that the Ar group remains equatorially disposed, then proper aldolization will materialize in only one of the four possible diastereomers. Experimental tests that are provided for three of the models are shown to conform to expectations. This analysis of the origin of stereoselectivity has, for the first time, defined the scope and limitations associated with C-ring closure by means of the aldol protocol.

  DOI：

  10.1021/jo981749j
• 作为产物：
  描述：

  (2S,4R,5S)-2-(4-Methoxy-phenyl)-5-(2-trimethylsilanyl-ethoxymethoxy)-4-vinyl-[1,3]dioxane-5-carbaldehyde 在 吡啶 、 咪唑 、 4-二甲氨基吡啶 、 氢氧化钾 、 四氧化锇 、 正丁基锂 、 18-冠醚-6 、 thexylborane 、 双氧水 、 sodium hexamethyldisilazane 、 双(三甲基硅烷基)氨基钾 、 戴斯-马丁氧化剂 作用下， 以 二氯甲烷 、 N,N-二甲基甲酰胺 为溶剂， 反应 18.08h， 生成 [(2S,4R,5S)-5-[(1S,2S,4S,5S,7R,8S)-2-(tert-Butyl-dimethyl-silanyloxy)-1-hydroxy-7-methoxymethoxy-5,11,11-trimethyl-6-oxo-bicyclo[6.2.1]undec-4-yl]-2-(4-methoxy-phenyl)-5-(2-trimethylsilanyl-ethoxymethoxy)-[1,3]dioxan-4-yl]-acetaldehyde
  参考文献：
  名称：

  Stereochemical Models for the Enantiocontrolled Construction of Fully Functionalized C Rings via Intramolecular Aldolization in Advanced Precursors to Paclitaxel

  摘要：

  Six transition-state models for intramolecular aldol C-ring annulation in suitably substituted bicyclo-[6.2.1]undecanones have been defined. The first consideration is the inherent conformational flexibility of the nine-membered ketonic ring which does not limit effective deprotonation to a single C-8 epimer. When the oxygen substituents at C-4 and C-5 are not covalently linked, the configuration at C-5 defines the stereochemical course of the ring closure, with only the beta series being amenable to the proper elaboration of paclitaxel. When C-4 and C-5 are incorporated into a 1,3-dioxane ring instead, the principal stereocontrol element is translocated into the aryl-substituted carbon of the cyclic acetal. To the extent that the Ar group remains equatorially disposed, then proper aldolization will materialize in only one of the four possible diastereomers. Experimental tests that are provided for three of the models are shown to conform to expectations. This analysis of the origin of stereoselectivity has, for the first time, defined the scope and limitations associated with C-ring closure by means of the aldol protocol.

  DOI：

  10.1021/jo981749j