Non‐natural Photoenzymatic Controlled Radical Polymerization Inspired by DNA Photolyase

Abstract Inspired by DNA photolyase, a non‐natural photoenzymatic catalysis of common flavoproteins is developed for controlled radical polymerization under irradiation of visible light. This photoenzymatic polymerization is highly efficient under mild conditions, applicable to various monomer families, suitable for both homogeneous and heterogeneous media, and can be externally modulated by switching light on and off. A unique combination of the natural enzymatic deoxygenation with the non‐natural photoenzymatic process enables an unprecedented oxygen‐tolerant, visible‐light‐controlled radical polymerization using a single enzyme to be developed. Visible light activation of non‐natural catalytic functions of the widely distributed flavoproteins is an exciting conceptual advance and may uncover a hitherto underexplored field of photoenzymatic catalysis.