Photoenzymatic Csp³-Csp³ bond formation via enzyme-templated radical-radical coupling.

ABSTRACT: Cross-couplings are essential reactions in modern chemical synthesis, enabling the rapid construction of complex molecules from simple precursors. Transition metal catalysts are prized for these transformations because their reactivity and selectivity can be tuned via judicious selection of the metal and ligand. Although enzymes offer analogous opportunities for tuning via protein engineering, their application to cross-coupling remains limited, as nature relies on alternative paradigms for building molecular complexity. Here, we report the cross-coupling of alkyl halides and benzylic carboxylic acids using an engineered flavin-dependent lactate monooxygenase-a photoenzyme. The enzyme achieves this feat by exploiting the redox versatility of the flavin cofactor. Stoichiometric experiments,

SUBMITTER: Liu Y 

PROVIDER: S-EPMC12888799 | biostudies-literature | 2026 Feb

REPOSITORIES: biostudies-literature