Rearrangement of acyclic-alkyl [3.2.1]bicyclic alcohols to free methylene dimethyl alkyl [2.2.2]bicyclic octanes: application to preparation of stereospecific novel sesquiterpene and terpenoids

摘要

Reaction of camphor-derived [3.2.1]bicyclic hydroxyl ketone with organolithium or Grignard reagents provided various alkyl/aryl [3.2.1]bicyclic diols, in which the secondary hydroxyl group was then protected and various acetoxy [3.2.1]bicyclic alcohols were obtained. Treatment of these acetoxy [3.2.1]bicyclic alcohols with TsOH in methanol at reflux afforded various methylene dimethyl alkyl/aryl [2.2.2]bicyclic octanes. For the application of the title reaction, some of these octanes were converted to stereospeciflc novel sesquiterpene and terpenoids. (C) 2015 Elsevier Ltd. All rights reserved.