A) Additions of thiols to 7-azanorbornadienes by a free radical pathway leads to nitrogen-directed homoallylic rearrangements to give 2-azanorborn-5-enes. Barton deoxygenation of 7-azabenzonorbornenols leads by a novel radical neophyl rearrangement to 2-azabenzonorbornenes.

B) An approach to the total synthesis of the fungal metabolite FR901483 (1) will be presented. Key steps include base-induced cyclization of an iodoamide intermediate leading to a bicyclic structure 3, as well as installation of the p-methoxybenzyl group by addition of the corresponding Grignard reagent to an N-acyliminium ion and the construction of the pyrrolidine ring by electrophilic cyclization to give 2. Particular focus will be on some of the peculiar stereochemical results obtained.

C) The synthesis of a range of ambiphilic derivatives containing both phosphine and borane moieties will be described. Initial explorations into their use in bifunctional organocatalysis and as ligands in organometallic chemistry will also be presented, with special attention paid to structure-activity relationships.