Asymmetric enzymatic hydrophosphorylation through O(2) activation.

A flavin-dependent enzyme enables highly enantioselective asymmetric hydrophosphorylation through O2 activation, producing phosphorus-containing compounds with high selectivity.

• Why it matters: Biocatalytic access to phosphorus-containing compounds is limited due to the rarity of enzymatic carbon-phosphorus bond formation, which constrains pharmaceutical and agrochemical development.
• What they did: The study used a repurposed flavin-dependent enzyme to convert reactive oxygen species into phosphorus-centered radicals, facilitating radical addition and hydrogen atom transfer with high enantioselectivity, and accommodating diverse phosphorus-hydrogen donors.
• The result: This work broadens biocatalysis to include programmable carbon-phosphorus bond formation, establishing a new paradigm for harnessing oxygen reactivity in enzymes to synthesize valuable phosphorus scaffolds.