Synthesis and Bridgehead Reactivities of 1-Substituted Tricyclo3,6>octanes

Article abstract of DOI:10.1021/jo00339a013

Ten bridgehead 1-substituted tricyclo<3.2.1.0^3,6>octanes were conveniently synthesized by our newly developed route.Thus, 5-allyl-5-(carboethoxy)cyclopentenone was irradiated to give a mixture of the tricyclic keto esters 5a and 5b, which were converted to 1-(carboethoxy)tricyclo<3.2.1.0^3,6>octane by the reduction of the corresponding thioketals.The ester function was then transformed to various substituents.The pK_a of the bridgehead carboxylic acid was determined.The bridgehead radical reactivity was also examined.The results were compared with those of the related systems.