(R)-3-{(S)-4-[(1S,2S,4S,5R,7R,8S)-2-(tert-Butyl-dimethyl-silanyloxy)-1-hydroxy-7-methoxymethoxy-5,11,11-trimethyl-6-oxo-bicyclo[6.2.1]undec-4-yl]-2,2-dimethyl-[1,3]dioxolan-4-yl}-3-(4-methoxy-benzyloxy)-propionaldehyde | 171625-72-2

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯酚醚
• 英文名称: (R)-3-{(S)-4-[(1S,2S,4S,5R,7R,8S)-2-(tert-Butyl-dimethyl-silanyloxy)-1-hydroxy-7-methoxymethoxy-5,11,11-trimethyl-6-oxo-bicyclo[6.2.1]undec-4-yl]-2,2-dimethyl-[1,3]dioxolan-4-yl}-3-(4-methoxy-benzyloxy)-propionaldehyde
• 英文别名: (3R)-3-[(4S)-4-[(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]-3-[(4-methoxyphenyl)methoxy]propanal
• CAS: 171625-72-2
• 化学式: C₃₈H₆₂O₁₀Si
• 分子量: 706.99
• InChiKey: ASKRSBOCESMMCN-RPFQTDTBSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.46
• 重原子数：
  49
• 可旋转键数：
  14
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.79
• 拓扑面积：
  119
• 氢给体数：
  1
• 氢受体数：
  10

反应信息

• 作为反应物：
  描述：

  (R)-3-{(S)-4-[(1S,2S,4S,5R,7R,8S)-2-(tert-Butyl-dimethyl-silanyloxy)-1-hydroxy-7-methoxymethoxy-5,11,11-trimethyl-6-oxo-bicyclo[6.2.1]undec-4-yl]-2,2-dimethyl-[1,3]dioxolan-4-yl}-3-(4-methoxy-benzyloxy)-propionaldehyde 在 sodium hydroxide 作用下， 以 四氢呋喃 、 甲醇 为溶剂， 反应 12.0h， 以85%的产率得到(2'R,4S,4'S,4'aS,6'R,7'S,10'S,11'S,12'aS)-11'-(tert-Butyldimethylsiloxy)dodecahydro-4',10'-dihydroxy-2'-[(p-methoxybenzyl)oxy]-6'-(methoxymethoxy)-2,2,4'a,13',13'-pentamethylspiro(1,3-dioxolane-4,1'(5'H)-[7,10]methanobenzocyclodecen)-5'-one
  参考文献：
  名称：

  An Abbreviated, Highly Stereocontrolled Route to Precursors of Taxol. Elaboration of a Fully Functionalized C Ring by Means of Intramolecular Aldol Cyclization

  摘要：

  The asymmetric synthesis of an advanced taxol precursor is reported. The scheme involves the conversion of (R)-glyceraldehyde acetonide into the Q-vinyl iodide 2, transmetalation of this intermediate, and 1,2-addition to the D-camphor derivative 11 from the endo direction. This convergent coupling gives rise to exo alcohol 12, which undergoes anionic oxy-Cope rearrangement at low temperatures. In situ methylation of the resulting enolate anion delivers 13, which is chemoselectively transformed into aldehyde 18. In a key step, the aldol cyclization of 18 proceeds without beta-elimination to deliver a tricyclic product in which proper absolute configuration is adopted at the two stereogenic centers being newly introduced. Following protection of the hydroxyl substituent as in 19b,the alpha-hydroxy ketone 21 is heated with aluminum tri-tert-butoxide in benzene in order to effect near-quantitative rearrangement to the taxol-like isomer 22.

  DOI：

  10.1021/jo00129a027
• 作为产物：
  描述：

  (1S,2S,3R,4S)-2-((Z)-2-{(S)-4-[(R)-1-(4-Methoxy-benzyloxy)-allyl]-2,2-dimethyl-[1,3]dioxolan-4-yl}-vinyl)-3-methoxymethoxy-7,7-dimethyl-1-vinyl-bicyclo[2.2.1]heptan-2-ol 在 吡啶 、 咪唑 、 sodium hydroxide 、 四氧化锇 、 sodium dithionite 、 2,3-二甲基-2-丁烯 、 硼烷四氢呋喃络合物 、 草酰氯 、 18-冠醚-6 、 双氧水 、 双(三甲基硅烷基)氨基钾 、 二甲基亚砜 、 三乙胺 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 10.33h， 生成 (R)-3-{(S)-4-[(1S,2S,4S,5R,7R,8S)-2-(tert-Butyl-dimethyl-silanyloxy)-1-hydroxy-7-methoxymethoxy-5,11,11-trimethyl-6-oxo-bicyclo[6.2.1]undec-4-yl]-2,2-dimethyl-[1,3]dioxolan-4-yl}-3-(4-methoxy-benzyloxy)-propionaldehyde
  参考文献：
  名称：

  An Abbreviated, Highly Stereocontrolled Route to Precursors of Taxol. Elaboration of a Fully Functionalized C Ring by Means of Intramolecular Aldol Cyclization

  摘要：

  The asymmetric synthesis of an advanced taxol precursor is reported. The scheme involves the conversion of (R)-glyceraldehyde acetonide into the Q-vinyl iodide 2, transmetalation of this intermediate, and 1,2-addition to the D-camphor derivative 11 from the endo direction. This convergent coupling gives rise to exo alcohol 12, which undergoes anionic oxy-Cope rearrangement at low temperatures. In situ methylation of the resulting enolate anion delivers 13, which is chemoselectively transformed into aldehyde 18. In a key step, the aldol cyclization of 18 proceeds without beta-elimination to deliver a tricyclic product in which proper absolute configuration is adopted at the two stereogenic centers being newly introduced. Following protection of the hydroxyl substituent as in 19b,the alpha-hydroxy ketone 21 is heated with aluminum tri-tert-butoxide in benzene in order to effect near-quantitative rearrangement to the taxol-like isomer 22.

  DOI：

  10.1021/jo00129a027