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

ABSTRACT

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 H ₂ O ₂ to catalyze the regioselective hydroxylation of tetradecanoic acid (C ₁₄ ). 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 H ₂ O ₂ 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.