bisaryl BenzP*Fe(II) species (i.e., without promoting chiral ligand dissociation) that are responsible for radical generation and C-C bond formation, respectively. 11f, At the same time, this iron mechanistic manifold would permit electron-rich tert-butyl radical to add regioselectively to the electron-deficient vinyl boronate to form a stabilized a-boryl radical. 11f In turn, effective capture of a-boryl radical with chiral mono-aryl BenzP*Fe(II) species could lead to enantioselective C-C bond formation. Gratifyingly, after extensive experimentation (see Supporting Information), we identified the use of Fe(acac)3 and (R,R)-BenzP* L1 as suitable combination to form the desired multicomponent cross-coupling product 4 in good yield (56%) and enantioselectivity (80:20 er) (entry 1). Notably, despite the complexity of three-components and potential side products arising from the formation of alkyl radicals in the presence of organometallic reagents and potentially redox active iron species (i.e., H-atom transfer, b-hydride elimination, polymerization, two-component cross-coupling, etc.) the observed enantioselectivities are up to par with current state-of-the-art two-component iron-catalyzed cross-coupling reactions. Moreover, as shown in entry 2, changing the alkyl radical precursor to tert-butyl iodide decreased both the yield and enantioselectivity while using chiral bisphosphine ligand L2 slightly improved enantioselectivity but decreased product yield (entries 2-3). Ligands that proved effective in related nickel-catalyzed transformations by Morken 12 and Nevado 13 were also less effective in this iron-catalyzed transformation (entries 4 and 5). In addition to the choice of ligand, we also found a drastic effect imposed by the precatalysts on both the yield and enantioselectivity. Specifically, while iron(III0 halide salts (FeBr3 and FeCl3) provided no enantiocontrol, FeBr2 was significantly less effective than Fe(acac)3 (entries 6-8). The use of other ethereal solvents, including non-coordinating solvent 2-Me-THF, which is known to accelerate transmetallation of mono-aryl BenzP*Fe(II) to the corresponding, and non-selective, bisaryl BenzP*Fe(II), led to significantly lower enantioselectivity (entries 9-10). These results are consistent with the role of solvent in controlling iron speciation and, as a consequence, enantioselectivity in BenzP*-iron catalyzed cross-couplings. Presumably, as non-coordinating solvents decrease the concentration of the mono-aryl BenP*Fe(II) species that is required for trapping alkyl radicals and promote enantioselectve C-C bond formation (vide infra). Consistent with this hypothesis, dimethylacetamide (DMA), a strongly coordinating solvent, significantly improved the enantioselectivity (up to 91:9) but decrease the product yields (only 19% of the desired crosscoupled product). A palladium precatalyst was also used to examine potential catalytic activity this reaction but did not yield the desired product (entry 14). Finally, control experiments confirmed the necessity of both the iron precatalyst and the ligand to drive the enantioselective multicomponent transformation (entries 15-17). Thus, after extensive screening, we move forward with BenzP* in this transformation given the balance initial three-component product yield and enantioselectivity for further substrate exploration.