We initiated our investigation into asymmetric C(sp 3 )-C(sp 3 ) cross-coupling using ethyl gemborazirconocene with NHPI ester 1a under blue light-emitting diodes (LEDs) irradiation. After extensive screening of Ni catalysts, chiral ligands, additives, and solvents (for detailed optimization studies, see Supplementary Table ), the best result was obtained affording 3a in 76.0% isolated yield and 91.0% enantiomeric excess (ee). However, the use of long-chained gem-borazirconocene alkanes led to diminished enantioselectivity. Recognizing the critical role of ancillary ligand in modulating reaction crossselectivity, and enantioselectivity, we focused on ligand optimization for octyl gem-borazirconocene with NHPI ester 1a. A series of diamine ligands were examined, and the desired C(sp 3 )-C(sp 3 ) cross-coupling was successfully achieved in the presence of Ni(BF4)•6H2O (10 mol%), chiral ligand L6 (12 mol%), tetrahydrofuran (THF, 0.1 M) under 0.5 W blue LEDs irradiation at 4ºC, yielding chiral alkylboron product 4b in 82.0% isolated yield and 91.6% ee (Table , entry 1 and Supplementary Table ). Control experiments confirmed the necessity of the Ni catalyst, visible light, and gem-borazirconocene alkanes for optimal reaction performance (Table , entries 2-4 and Supplementary Figure ). Ligands with different substitutions at nitrogen atoms (L1, L2, L3) or different aryl groups (L4, L5, L7) were found to be less effective than L6 (Table , entries 4-10).