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Cross-coupling reactions are among the most important transformations in modern organic synthesis1–3. Although the range of reported (het)aryl halides and nucleophile coupling partners is very large considering various protocols, the reaction conditions vary considerably between compound classes, necessitating renewed case-by-case optimization of the reaction conditions4. Here we introduce adaptive dynamic homogeneous catalysis (AD-HoC) with nickel under visible-light-driven redox reaction conditions for general C(sp2)–(hetero)atom coupling reactions. The self-adjustive nature of the catalytic system allowed the simple classification of dozens of various classes of nucleophiles in cross-coupling reactions. This is synthetically demonstrated in nine different bond-forming reactions (in this case, C(sp2)–S, Se, N, P, B, O, C(sp3, sp2, sp), Si, Cl) with hundreds of synthetic examples under predictable reaction conditions. The catalytic reaction centre(s) and conditions differ from one another by the added nucleophile, or if required, a commercially available inexpensive amine base.

A broadly applicable method for the trifluoromethylthiolation of methylene C(sp3)–H, methine C(sp3)–H, α-oxygen C(sp3)–H, and formyl C(sp2)–H bonds is presented using the decatungstate anion as the sole catalyst. By adjusting the substrate ratio and reaction concentration, this method was applied to 40 examples in good regioselectivities, including the derivatization of natural products. Furthermore, SCF3–drug analogues were synthesized by subsequent functionalization of the SCF3products, highlighting the importance of this photocatalyzed C–H functionalization.