To evaluate the feasibility of our designed multicomponent strategy, we selected N-vinylphthalimide (1a), 2-(2-bromo-1,1,2,2-tetrafluoroethoxy) anisole (2a) and 3-methoxyphenylmagnesium bromide (3a) as the model substrates (Table ). Pleasingly, using dcpe and FeCl3, we were able to observe the formation of the desired product in good yield (60%) (entry 1). Remarkably, the alcohol product of the nucleophilic addition of 3a over 1a was observed only in very low yield (∼10%). In addition, we screened different iron sources (entries 2-3) and found that FeCl3 gives the best yield for the reaction. Finally, to assess the ligand effect on this MC-CCR, we screened several commercially available bidentate ligands (entries 4-9). Notably, only 1,2-bis(diisopropylphosphino)ethane (dippe) also led to a high yield (63%, entry 9) as with the dcpe ligand. Notably, we observed that increasing the loading of Grignard reagent (added via a syringe pump over the course of 1 h) improved the overall yield (up to 70%) (entry 10). Finally, the reaction proceeded smoothly even with only 5 mol % of FeCl3 albeit with reduced yield (entry 11). Additional control experiments (entries 12-13) confirmed that both iron salt and ligand are essential to promote the MC-CCR. In this context, we attribute the reactivity to form 4a to a unique bisphosphineiron catalytic system, that under slow addition of Grignard reagent, generates the active mono-aryl and bis-aryl bisphosphine iron(II) species that are responsible for C-C bond formation and radical generation, respectively. 9d Overall, the optimized conditions were consisted of performing the reaction in THF at 0 ºC in the presence of FeCl3 (10 mol %) and using dcpe (20 mol %). Under these optimized conditions (See Supporting Information for full screening details), the three components adduct 4a was isolated in 60% yield (dcpe).