Regioselective C-H Oxyfunctionalization of Aliphatic Acids Through a Consecutive Biosolar Cascade.

The fusion of photocatalysis and biocatalysis has recently emerged as a promising avenue for selective oxidative transformations. Herein, we report a self-sustained biosolar reaction platform that integrates binary alkali-metal-doped carbon nitride (ACN) with a cytochrome P450 enzyme (peroxygenase CYP152A1). The sodium-potassium co-doped ACN (NaK-ACN) photocatalyst exhibits an enhanced surface built-in electric field, arising from the synergistic effects of the alkali metal dopants, enabling an efficient two-electron oxygen reduction reaction (2e- ORR) under visible-light irradiation. Concurrently, CYP152A1 rapidly consumes the in situ generated H2O2 to catalyze the regioselective hydroxylation of tetradecanoic acid (C14). This light-driven cascade achieved α- and β-hydroxylation activities 37.8 and 39.2 fold higher than those of conventional systems relying on an exogenous H2O2 supply. Collectively, this study establishes a biosolar cascade that couples the photocatalytic oxygen reduction reaction with regioselective enzymatic oxyfunctionalization, providing a versatile platform for solar-driven oxidation of aliphatic substrates.