Direct Boron‐10 Access: Nickel‐Catalyzed Reductive C(sp²)─¹⁰B Coupling Utilizing ¹⁰BF₃

The boron‐10 isotope ( 10 B) is critical for boron neutron capture therapy (BNCT); however, the direct use of industrially available 10 BF 3 for synthesizing 10 B‐enriched compounds remains challenging due to the strong B─F bonds. Herein, we present a nickel‐catalyzed reductive protocol that enables direct C(sp 2 )─ 10 B bond formation using 10 BF 3 . This approach employs AlCl 3 and a Lewis base to generate electrophilic borenium ions in situ. The method eliminates the need for pre‐functionalized boron reagents, providing an efficient route to diverse 10 B‐enriched compounds with promising applications in BNCT and neutron‐shielding materials.