Enantioselective heteroatom-directed C(sp(3))-H borylation reactions of 2-aminopyridines and 2-alkylpyridines with Rh-and Ir catalytic systems using commercially available chiral monophosphine ligands, respectively, were developed. This methodology provides an innovative example of a homogeneous catalytic system for C(sp(3))-H borylation, and allows the direct synthesis of optically active alkylboronates with a moderate level of enantioselectivity.