(1S,2S,3R,4S)-2-<(R)-3-<(2-Methoxyethoxy)methoxy>-1-cyclohexen-1-yl>-3-(methoxymethoxy)-1-<(E)-2-(p-methoxyphenoxy)vinyl>-7,7-dimethyl-2-norbornanol | 162790-73-0

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯酚醚
• 英文名称: (1S,2S,3R,4S)-2-<(R)-3-<(2-Methoxyethoxy)methoxy>-1-cyclohexen-1-yl>-3-(methoxymethoxy)-1-<(E)-2-(p-methoxyphenoxy)vinyl>-7,7-dimethyl-2-norbornanol
• 英文别名: (1S,2S,3R,4S)-2-[(3R)-3-(2-methoxyethoxymethoxy)cyclohexen-1-yl]-3-(methoxymethoxy)-1-[(E)-2-(4-methoxyphenoxy)ethenyl]-7,7-dimethylbicyclo[2.2.1]heptan-2-ol
• CAS: 162790-73-0
• 化学式: C₃₀H₄₄O₈
• 分子量: 532.675
• InChiKey: HWCBANACNIUBGX-YDFKBUHCSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.5
• 重原子数：
  38
• 可旋转键数：
  14
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.67
• 拓扑面积：
  84.8
• 氢给体数：
  1
• 氢受体数：
  8

反应信息

• 作为反应物：
  描述：

  (1S,2S,3R,4S)-2-<(R)-3-<(2-Methoxyethoxy)methoxy>-1-cyclohexen-1-yl>-3-(methoxymethoxy)-1-<(E)-2-(p-methoxyphenoxy)vinyl>-7,7-dimethyl-2-norbornanol 、 碘甲烷 在 18-冠醚-6 、 氧气 、 双(三甲基硅烷基)氨基钾 作用下， 生成 (1R,4aS,6R,7S,10E,12S,12aR)-2,3,4,4a,6,7,8,9,12,12a-Decahydro-4a-methoxy-1-<(2-methoxyethoxy)methoxy>-6-(methoxymethoxy)-12-(p-methoxyphenoxy)-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-<<<3-Bromo-2-cyclohexen-1-yl>oxy>methoxy>-2-methoxyethane 、 (1S,3R,4S)-3-(Methoxymethoxy)-1-<(E)-2-(p-methoxyphenoxy)vinyl>-7,7-dimethyl-2-norbornanone 在 叔丁基锂 作用下， 以 四氢呋喃 为溶剂， 以84%的产率得到(1S,2S,3R,4S)-2-<(R)-3-<(2-Methoxyethoxy)methoxy>-1-cyclohexen-1-yl>-3-(methoxymethoxy)-1-<(E)-2-(p-methoxyphenoxy)vinyl>-7,7-dimethyl-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