Starting from methyl 6-O-allyl-4-azido-2,3-di-O-benzyl-4-deoxy-α-D-galactopyranoside, four new derivatives containing 2-iodobenzamido and 3-(iodoacetamido)benzamido groups were synthesized. These four compounds were submitted to tri-n-butyltin hydride mediated radical cyclization reactions, resulting in two macrolactams from 11- and 15-endo aryl radical cyclization. The corresponding four hydrogenolysis products were also obtained. The structures of the new compounds were elucidated by ¹H and 13C NMR spectroscopy, DEPT, COSY, HMQC and HMBC experiments.

This review presents natural, semi-synthetic and synthetic bioactive macrolactams and their structure-activity relationships when available. For macrolactams in clinical use the advantages and disadvantages in relation to other drugs are presented, and for synthetic macrolactams the method used in the cyclization is showed. Regarding macrocyclic synthesis by the tri-n-butyltin hydride-mediated radicalar carbocyclization reaction the precursor, the reaction conditions, products and yields, mechanism and cyclization mode are discussed.