A wide range of N-alkyl anilines proved effective under the optimized conditions, providing the alkylation products in generally good yields and excellent selectivity (Fig. ). A remarkable feature of this CDs photocatalytic system was its notable tolerance to unprotected N-H bonds, a characteristic uncommon in radical mediated photoredox C(sp3)-H bond functionalization (ref 49, 50). Both electron-rich and electron-deficient anilines formed the corresponding products in good yields (Fig. ). Various functional groups, including halide, trifluoromethyl, acyl, benzoate ester, free carboxylic acid, and nitrile groups, were well tolerated. Steric hindrance had little impact on reactivity, bulky groups such as phenyl, carboxy, and carboxylate ester groups afforded products in good to moderate yields . Notably, the catalytic system exhibited remarkable chemoselectivity toward the N-methyl C-H bonds. For the N-methyl anilines also bearing other C-H bonds, such as benzylic, heteroatom α C-H bonds (BDE = 89-92 kcal/mol) (ref 51), we were not able to identify notable alkylation products on these competitive positions in all experiments . For substrates containing two alkyl groups on the aniline nitrogen, excellent regioselectivity on methyl C-H was observed, as evidenced by the formation of sole products in good yields , while the N-ethyl and N-benzyl C-H bonds remained intact. Additionally, other electron-deficient alkenes could also serve as the radical trap in this CD-1 photoredox catalytic system .