(1S,3aS,4R,5S,6aS,9aS,10aR)-1,4-Dimethyl-dodecahydro-dicyclopenta[a,d]cyclooctene-5,9a-diol | 134153-13-2

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (1S,3aS,4R,5S,6aS,9aS,10aR)-1,4-Dimethyl-dodecahydro-dicyclopenta[a,d]cyclooctene-5,9a-diol
• CAS: 134153-13-2
• 化学式: C₁₆H₂₈O₂
• 分子量: 252.397
• InChiKey: NDHLHTRUWYKLPR-FYFPFLJLSA-N

反应信息

• 作为产物：
  描述：

  (Z)-(3aR,6S,6aR,9R,9aS)-6,9-Dimethyl-2,3,3a,4,6,6a,7,8,9,9a-decahydro-1H-dicyclopenta[a,d]cycloocten-5-one 在 二异丁基氢化铝 lithium aluminium tetrahydride 、 间氯过氧苯甲酸 作用下， 以 乙醚 、 正己烷 、 二氯甲烷 、 苯 为溶剂， 反应 22.0h， 生成 (1S,3aS,4R,5S,6aS,9aS,10aR)-1,4-Dimethyl-dodecahydro-dicyclopenta[a,d]cyclooctene-5,9a-diol
  参考文献：
  名称：

  Alkylaluminum-catalyzed Claisen expansion reactions. Scope and stereochemistry

  摘要：

  The triisobutylaluminum-catalyzed Claisen rearrangement of a series of bicyclic allyl vinyl ethers was examined in connection with a planned synthesis of the diterpene epoxydictymene. The exocyclic vinyl ethers studied undergo [3,3] sigmatropy via chairlike transition states to provide products having Z stereochemistry about the double bond of the eight-membered ring. Differences appear only in the extent of stereoselectivity in the ensuing carbonyl reduction step. Two companion endocyclic vinyl ethers were found to utilize boat transition states to deliver Z products exclusively. In all cases, the level of chirality transfer is excellent. An analysis is presented showing that the relative configurations of the newly generated stereogenic centers, established in several key examples by X-ray crystallography, follow directly from the boat-chair options, both of which have the latent ability to be influenced catalytically by (i-Bu)3Al.

  DOI：

  10.1021/jo00012a014