Gram-scale, enantiospecific total syntheses of the anti-leukemia marine natural products kapakahines B and F have been completed. Two powerfully simplifying transformations have enabled the gram-scale synthesis of this natural product family: (1) an oxidative N-C bond-forming reaction that sets a key quaternary center with comptete stereocontrol and (2) a unique strategy for the construction of twisted macrocycles via dynamic equilibration of complex late-stage intermediates.