With several Ala B derivatives in hand, we next investigated if these primary nucleophiles could participate in Pd-catalyzed Suzuki-Miyaura cross-coupling reactions (Table ). Curiously, previous studies did not report if Ala B could participate in either radical or two-electron C-C bond-forming processes. The initial optimization studies identified BPai ester 30 with PdCl2 (10 mol%), K2CO3 (3 equiv.), Ag2O (2 equiv.) in 1,4-dioxane at 100 °C and a monodentate phosphine ligand as a promising catalytic system (entries 1-5). JackiePhos (entry 2) optimized to promote rapid transmetalation of Ala Sn reagents furnished low yield of 32 (15%), whereas SPhos (entry 3) and XPhos (entry 4) resulted in encouraging albeit suboptimal yields (47-48%). Based on these initial screening studies, we next turned to diphosphines, among which dppf was identified as the most efficient ligand (entries 6-14). We found that moderate yields were obtained for reactions with K2CO3 (entry 5) and Cs2CO3 (entry 8) but slight improvement was observed for K3PO3 and KF (entries 6 and 7). Pd(II) as the precursor for this transformation was consistently superior when compared to the efficiency of the reaction catalyzed by Pd(0) (entry 9) as well as to the conditions where excess of the electrophile 31 was used (entry 10). Because even after 24 h 4-bromobiphenyl 31 was not completely consumed, we elected to change silver additive to Ag2CO3 (entry 11), extend the reaction time to 48 h (entry 12) and increase the amount of Ala B to 2 equivalents (entry 13) which resulted in 83% yield of alanine derivative 32 (entry 14). Under the optimized conditions, we modified the solvent and used THF, which allowed us to lower the reaction temperature to 70 °C. Other solvent systems including MeCN or 2-methyltetrahydrofuran gave lower yields, but a 4:1 mixture of THF and H2O was compatible with the substrate but afforded 32 in lower yields (56%; for details, see the SI).