To further rationalize the Cp2Zr III Cl mediated reduction of NHPI esters, the DFT computations of this process was conducted. The results showed that the NHPI ester initially bound to the Cp2Zr III Cl complex, forming a stable intermediate RG_cpx (Figure ). The spin density plot revealed that the unpaired In conclusion, we have developed an asymmetric decarboxylative C(sp 3 )-C(sp 3 ) cross-coupling reaction between primary aliphatic acids and gem-borazirconocene alkanes, providing a practical access to a broad range of valuable chiral alkylboron products using readily available primary aliphatic acids feedstocks. The high functional group tolerance allowed for late-stage modification of bioactive molecules and natural products with excellent enantioselectivity, highlighting the potential utility of this protocol. The intrinsic photoreactivity of alkylzirconocene reagents and their potential for enantioconvergent radical cross-coupling are harnessed in the asymmetric decarboxylative C(sp 3 )-C(sp 3 ) cross-coupling reaction, offering a synthetically valuable strategy for photoredox chemistry. mL), at 4°C with 0.5 W blue LEDs for 24 h. [ a ] Unless otherwise mentioned, all optimization reactions were carried out on a 0.1 mmol scale. The yields were determined by GC-MS analysis of the crude samples using dodecane as the internal standard. [ b ] The yield is the isolated yield (0.2 mmol scale). The ee value was detected by HPLC. N.D.: not detected.