The enantioselective synthesis of atropisomeric, tribrominated benzamides and subsequent regioselective transformations to afford derivatized, axially chiral molecules is reported. The enantioenriched tribromides were carried through sequential Pd-catalyzed cross-coupling and lithium-halogen exchange with high regioselectivity and enantioretention. A variety of complexity-generation functional group installations were performed to create a library of homochiral benzamides. The potential utility of these molecules is demonstrated by using a phosphino benzamide derivative as an asymmetric ligand in a Pd-catalyzed allylic alkylation.