Abstract
<jats:p>Gaseous alkanes constitute the most abundant carbon feedstock, yet their direct utilization in synthesis remains challenging due to their gaseous nature and the inertness of their C(sp3)–H bonds. Regioselective functionalization of C3 and C4 alkanes, such as propane and n-butane, poses an additional significant challenge. Herein, we report a dual TBADT/nickel catalytic platform that departs from conventional photocatalytic hydrogen atom transfer (HAT) strategies, where site-selectivity is dictated by the HAT step. Instead, as demonstrated by DFT studies, regioselectivity is controlled post-HAT through a radical-locking mechanism in which the nickel co-catalyst serves as an alkyl radical reservoir, prolonging radical lifetime and selectively releasing the secondary radical while sequestering the primary one. This approach delivers excellent regioselectivity (>20:1 b:l) and broad applicability across Giese-type additions, alkene dicarbofunctionalizations, and defluorinative alkylations.</jats:p>