(1R,4aR,7R,10E,12R,12aR)-1-(Benzyloxy)-2,3,4,4a,6,7,8,9,12,12a-decahydro-12-(p-methoxyphenoxy)-13,13-dimethyl-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,7R,10E,12R,12aR)-1-(Benzyloxy)-2,3,4,4a,6,7,8,9,12,12a-decahydro-12-(p-methoxyphenoxy)-13,13-dimethyl-7,10-methanobenzocyclodecen-5(1H)-one
• 英文别名: (1R,4R,8R,9R,10R,11E)-10-(4-methoxyphenoxy)-15,15-dimethyl-8-phenylmethoxytricyclo[10.2.1.04,9]pentadec-11-en-3-one
• 化学式: C₃₁H₃₈O₄
• 分子量: 474.64
• InChiKey: WPZOSZSYEOWSBQ-UBBRRPSUSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.1
• 重原子数：
  35
• 可旋转键数：
  6
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.52
• 拓扑面积：
  44.8
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为产物：
  描述：

  对苯二甲醚 在 18-冠醚-6 正丁基锂 、 过氧化氢苯甲酰 、 cerium(III) chloride 、 五氯化磷 、 叔丁基锂 、 乙烯基-锂 、 双(三甲基硅烷基)氨基钾 作用下， 以 四氢呋喃 、 四氯化碳 、 正己烷 、 甲苯 、 正戊烷 、 苯 为溶剂， 反应 53.0h， 生成 (1R,4aR,7R,10E,12R,12aR)-1-(Benzyloxy)-2,3,4,4a,6,7,8,9,12,12a-decahydro-12-(p-methoxyphenoxy)-13,13-dimethyl-7,10-methanobenzocyclodecen-5(1H)-one
  参考文献：
  名称：

  A means for stereocontrolled introduction of the C-2 oxygen substituent in functionalized cis-tricyclo[9.3.1.03,8]pentadecanones related to taxol

  摘要：

  Several optically pure cis-tricyclo[9.3.1.0(3,8)]pentadecanones have been prepared via anionic oxy-Cope rearrangement of exo-norbornanol precursors that have been obtained by convergent coupling of two functionalized reaction partners. The sigmatropic rearrangement is shown to proceed with exceptionally good stereochemical transmission because of universal adherence to the same endo-chair transition state. The atropisomeric aspects of this pivotal transformation are addressed. Also investigated was the proclivity of the products to undergo transannular hemiketal formation following osmylation of the bridgehead double bond. As matters turn out, the operation or nonoperation of this intramolecular addition to the C-9 carbonyl group is amenable to control merely by adjusting properly the stereochemistry of a single pendant substituent.

  DOI：

  10.1021/jo00076a058

文献信息

• A means for stereocontrolled introduction of the C-2 oxygen substituent in functionalized cis-tricyclo[9.3.1.03,8]pentadecanones related to taxol
  作者：Leo A. Paquette、Scot K. Huber、Richard C. Thompson

  DOI：10.1021/jo00076a058

  日期：1993.11

  Several optically pure cis-tricyclo[9.3.1.0(3,8)]pentadecanones have been prepared via anionic oxy-Cope rearrangement of exo-norbornanol precursors that have been obtained by convergent coupling of two functionalized reaction partners. The sigmatropic rearrangement is shown to proceed with exceptionally good stereochemical transmission because of universal adherence to the same endo-chair transition state. The atropisomeric aspects of this pivotal transformation are addressed. Also investigated was the proclivity of the products to undergo transannular hemiketal formation following osmylation of the bridgehead double bond. As matters turn out, the operation or nonoperation of this intramolecular addition to the C-9 carbonyl group is amenable to control merely by adjusting properly the stereochemistry of a single pendant substituent.