(1S,2S,3R,4S)-2-<(S)-3-(tert-Butyldimethylsiloxy)-1-cyclohexen-1-yl>-3-(methoxymethoxy)-7,7-dimethyl-1-vinyl-2-norbornanol | 162790-60-5

• 分子结构分类: 有机化合物 - 有机金属化合物 - 有机类金属化合物
• 英文名称: (1S,2S,3R,4S)-2-<(S)-3-(tert-Butyldimethylsiloxy)-1-cyclohexen-1-yl>-3-(methoxymethoxy)-7,7-dimethyl-1-vinyl-2-norbornanol
• 英文别名: (1S,2S,3R,4S)-2-[(3S)-3-[tert-butyl(dimethyl)silyl]oxycyclohexen-1-yl]-1-ethenyl-3-(methoxymethoxy)-7,7-dimethylbicyclo[2.2.1]heptan-2-ol
• CAS: 162790-60-5
• 化学式: C₂₅H₄₄O₄Si
• 分子量: 436.707
• InChiKey: NTSGNECJXJZYGK-ZDSZSBLGSA-N

物化性质

• 沸点：
  446.1±45.0 °C(predicted)
• 密度：
  1.02±0.1 g/cm3(Temp: 20 °C; Press: 760 Torr)(predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  5.83
• 重原子数：
  30
• 可旋转键数：
  8
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.84
• 拓扑面积：
  47.9
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  (1S,2S,3R,4S)-2-<(S)-3-(tert-Butyldimethylsiloxy)-1-cyclohexen-1-yl>-3-(methoxymethoxy)-7,7-dimethyl-1-vinyl-2-norbornanol 在 18-冠醚-6 、 potassium hydride 作用下， 以 四氢呋喃 为溶剂， 以53%的产率得到(1S,4aR,6R,7S,10E,12aR)-2,3,4,4a,6,7,8,9,12,12a-Decahydro-1-hydroxy-6-(methoxymethoxy)-13,13-dimethyl-7,10-methanobenzocyclodecen-5(1H)-one
  参考文献：
  名称：

  Stereocontrolled Oxygenation of Camphor Derivatives as a Prelude to the Complete .beta.-Ring Functionalization of Potential Precursors to Taxol and Structural Analogs Thereof

  摘要：

  The possibility of realizing the predominant exo a-hydroxylation of camphor-related ketones is described. Both the direct oxidation of enolate anions with 1-phenyl-N-(phenylsulfonyl)oxaziridine or exposure of the derived silyl enol ethers to dimethyl dioxirane are conducive to exo attack. Following conversion to MOM derivatives, the acidity of the alpha-carbonyl proton is reduced sufficiently to allow direct condensation of these hindered ketones with cyclohexenyllithium reagents. The subsequent anionic oxy-Cope rearrangement of the resulting exo carbinols results in direct conversion to tricyclic products that feature the characteristic C-2,C-9,C-10 B-ring oxygenation pattern resident in taxol. Further, the stereogenic centers are introduced in their proper absolute configuration. The steric demands of the [3,3] sigmatropic shift are discussed and the stereochemical features conducive to the minimization of steric compression subjected to experimental verification.

  DOI：

  10.1021/jo00109a020
• 作为产物：
  描述：

  1-Bromo-3(S)-(tert-butyldimethylsiloxy)cyclohexene 、 (1S,4S)-3-(Methoxymethoxy)-7,7-dimethyl-1-vinyl-2-norbornanone 在 叔丁基锂 作用下， 以 四氢呋喃 、 正戊烷 为溶剂， 以73%的产率得到(1S,2S,3R,4S)-2-<(S)-3-(tert-Butyldimethylsiloxy)-1-cyclohexen-1-yl>-3-(methoxymethoxy)-7,7-dimethyl-1-vinyl-2-norbornanol
  参考文献：
  名称：

  Stereocontrolled Oxygenation of Camphor Derivatives as a Prelude to the Complete .beta.-Ring Functionalization of Potential Precursors to Taxol and Structural Analogs Thereof

  摘要：

  The possibility of realizing the predominant exo a-hydroxylation of camphor-related ketones is described. Both the direct oxidation of enolate anions with 1-phenyl-N-(phenylsulfonyl)oxaziridine or exposure of the derived silyl enol ethers to dimethyl dioxirane are conducive to exo attack. Following conversion to MOM derivatives, the acidity of the alpha-carbonyl proton is reduced sufficiently to allow direct condensation of these hindered ketones with cyclohexenyllithium reagents. The subsequent anionic oxy-Cope rearrangement of the resulting exo carbinols results in direct conversion to tricyclic products that feature the characteristic C-2,C-9,C-10 B-ring oxygenation pattern resident in taxol. Further, the stereogenic centers are introduced in their proper absolute configuration. The steric demands of the [3,3] sigmatropic shift are discussed and the stereochemical features conducive to the minimization of steric compression subjected to experimental verification.

  DOI：

  10.1021/jo00109a020