Abstract Homoleptic lithium tri-and tetraalkyl zincates were reacted with a set of bromopyridines. Efficient and chemoselective bromine–metal exchanges were realized at room temperature with a substoichiometric amount of nBu 4 ZnLi 2⋅ TMEDA reagent (1/3 equiv; TMEDA= N, N, N′, N′-tetramethylethylenediamine). This reactivity contrasted with that of tBu 4 ZnLi 2⋅ TMEDA, which was inefficient below one equivalent. DFT ...