Synthesis and Bridgehead Reactivities of 1-Substituted Tricyclo3,6>octanes
Ten bridgehead 1-substituted tricyclo3,6>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)tricyclo3,6>octane by the reduction of the corresponding thioketals.The ester function was then transformed to various substituents.The pKa of the bridgehead carboxylic acid was determined.The bridgehead radical reactivity was also examined.The results were compared with those of the related systems.