Abstract:
First part represents a new strategy toward the important class of benzomorphans. The key bond formation is based on an intramolecular Buchwald-Hartwig enolate arylation reaction. Thus, alkylation of piperidones with ortho-bromobenzyl bromides provides the necessary substrates. In the presence of a palladium catalyst, a sterically hindered phosphane ligand, and a base, carbon-carbon bond formation to tricyclic benzomorphan derivatives takes place. After removal of the N-protecting group, derivatization reactions are possible.
The second part of the dissertation contains the the preparation of the fully functionalized core structure of the antifungal macrolactone queenslandon using a novel strategy consisting of a glycolate aldol reaction and hydroboration of the corresponding enol ether followed by Suzuki cross-coupling with an iodostyrene. After conversion of the cross-coupling product to the seco acid, Mitsunobu macrolactonization and protecting group manipulations led to the queenslandon model compound.