Stereospecific Skeletal Rearrangement Reactions in Bridgehead-Substituted Bicyclo Systems under Neutral Conditions

Article abstract of DOI:10.1021/jo00388a031

General and stereospecific pinacolic-type rearrangement reactions of vicinal methoxy mesylates under neutral conditions have been developed for the construction of functionalized bicyclo<3.2.1>octanes.For instance, exo-5,5-dimethyl-1-methoxy-6-<(methylsulfonyl)oxy>bicyclo<2.2.2>oct-2-ene rearranged to 8,8-dimethylbicyclo<3.2.1>oct-6-en-2-one when treated with NaI in DMF.The tolerance of various functional groups to these reaction conditions was demonstrated in the transformation of the C ring of thebaine to the corresponding bicyclo<3.2.1>octenone.The quadroneskeleton (ABC rings) was also constructed by utilizing this pinacol-type rearrangement reaction.