(1R,4aR,6R,7S,10E,12R,12aR)-2,3,4,4a,6,7,8,9,12,12a-Decahydro-1-<(p-methoxybenzyl)oxy>-6-(methoxymethoxy)-12-(p-methoxyphenoxy)-4a,13,13-trimethyl-7,10-methanobenzocyclodecen-5(1H)-one

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: (1R,4aR,6R,7S,10E,12R,12aR)-2,3,4,4a,6,7,8,9,12,12a-Decahydro-1-<(p-methoxybenzyl)oxy>-6-(methoxymethoxy)-12-(p-methoxyphenoxy)-4a,13,13-trimethyl-7,10-methanobenzocyclodecen-5(1H)-one
• 英文别名: (1S,2R,4R,8R,9R,10R,11E)-2-(methoxymethoxy)-10-(4-methoxyphenoxy)-8-[(4-methoxyphenyl)methoxy]-4,15,15-trimethyltricyclo[10.2.1.04,9]pentadec-11-en-3-one
• 化学式: C₃₅H₄₆O₇
• 分子量: 578.746
• InChiKey: SWEPWAFJXVMDTO-RCMWUZGHSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.2
• 重原子数：
  42
• 可旋转键数：
  10
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.57
• 拓扑面积：
  72.4
• 氢给体数：
  0
• 氢受体数：
  7

反应信息

• 作为产物：
  描述：

  (1S,2S,3R,4S)-2-<(R)-3-<(p-Methoxybenzyl)oxy>-1-cyclohexen-1-yl>-3-(methoxymethoxy)-1-<(Z)-2-(p-methoxyphenoxy)vinyl>-7,7-dimethyl-2-norbornanol 、 碘甲烷 在 18-冠醚-6 、 六甲基二硅烷 、 potassium hydride 作用下， 生成 (1R,4aR,6R,7S,10E,12R,12aR)-2,3,4,4a,6,7,8,9,12,12a-Decahydro-1-<(p-methoxybenzyl)oxy>-6-(methoxymethoxy)-12-(p-methoxyphenoxy)-4a,13,13-trimethyl-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

文献信息

• Stereocontrolled Oxygenation of Camphor Derivatives as a Prelude to the Complete .beta.-Ring Functionalization of Potential Precursors to Taxol and Structural Analogs Thereof
  作者：Steven W. Elmore、Leo A. Paquette

  DOI：10.1021/jo00109a020

  日期：1995.2

  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.