Given that ~20% of drugs on the market contain at least one fluorine atom, combined with the lack of enantioselective three-component methods using vinyl borates and difluoroalkyl radical precursors, we were also interested in investigating the possibility of rapidly producing diverse fluorine-containing enantioeneriched alkylboron reagents (inset; Figure ). Indeed, in contrast to prior methods, fluorinated radical precursors were tolerated in the enantioselective iron-catalyzed multicomponent radical cross-coupling reaction, producing the enantioenriched fluorinated organoboron products (26, 27, and 28) albeit slightly lower yields and modest enantioselectivity were observed. Presumably, the lower yields are attributed to polarity mismatch between electron-deficient vinylB(pin) and electron-poor (poly)fluoroalkyl radicals that open opportunities for side reactions prior to undergoing the desired Giese addition to vinylB(pin). On the basis on prior experimental and mechanistic studies on Fe-catalyzed asymmetric cross-coupling reactions and multicomponent cross-coupling involving a-boryl radicals, 11f we turned to dispersion-corrected density functional theory (DFT) calculations to gain insight into the nature of C-C bond formation and the origin of enantioselectivity. We hypothesize that this shift in equilibrium can have pronounced effects in preventing deleterious and unwanted radical pathways stemming from non-coordinated a-boryl radicals (i.e., polymerization, Hatom abstraction, SET oxidation, etc.). Finally, Fe(III) IV intermediate is poised to undergo a rapid and enantioselective C-C bond to form the desired enantioenriched multicomponent product 4 and Fe(I) species that can then restart the catalytic cycle. 11a, 27 Further, consistent with the observed enantioselectivity, the energy difference between the lowest energy diastereomeric transition states for the reductive elimination step is ~1.0 kcal/mol (Figure ) in favor of the (S)-product. As shown in Figure , closer inspection of the lowest energy diastereomeric transition states revealed a favorable C-H---O interaction in TS S -IV-I, which is absent in the competing transition state leading to minor (R) product. In addition, the repulsion between the t Bu group and the Bpin group is more prominent in the transition state leading to the (R) product as evident from the NCI (Non-Covalent Interaction) plots.