The unification of Anion Relay Chemistry (ARC) with the Takeda and Hiyama palladium-mediated cross-coupling processes to provide aryl aryl, alkenyl aryl, and alkenyl alkenyl coupled products by exploiting a common silicon-based transfer agent has been achieved. These results provide a practical solution for intermolecular cross-coupling of organolithium reagents without the problematic lithium halogen exchange and/or undesired homocoupling that has kept organolithium cross-couplings from achieving the same level of utility as other palladium-mediated methods (e.g., Suzuki organoboron, Negishi organozinc, Stale organotin, Kumada organomagnesium, etc.).