H2 as Fuel for Flavin- and H2O2-Dependent Biocatalytic Reactions

Herein, we report a novel H₂-driven regeneration system for reduced flavin cofactors. Using an O₂-tolerant hydrogenase, we achieved NAD(P)H-independent, highly selective, ene-reductase-catalyzed C=C-double bond reductions, monooxygenase-catalyzed epoxidations and peroxygenase-catalyzed hydroxylations. The hydrogenase performed up to 46000 catalytic cycles and product titers of up to 22 mM have been accomplished. Overall, this system bears the promise to power flavin-dependent biocatalytic reactions with H₂ in a highly atom efficient manner.