Modifying Proton Relay into Bioinspired Dye‐Based Coordination Polymer for Photocatalytic Proton‐Coupled Electron Transfer

Abstract Proton‐coupled electron transfer (PCET) imparts an energetic advantage over single electron transfer in activating inert substances. Natural PCET enzyme catalysis generally requires tripartite preorganization of proton relay, substrate‐bound active center, and redox mediator, making the processes efficient and precluding side reactions. Inspired by this, a heterogeneous photocatalytic PCET system was established to achieve higher PCET driving forces by modifying proton relays into anthraquinone‐based anionic coordination polymers. The proximally separated proton relays and photoredox‐mediating anthraquinone moiety allowed pre‐assembly of inert substrate between them, merging proton and electron into unsaturated bonds by photoreductive PCET, which enhanced reaction kinetics compared with the counter catalyst without proton relay. This photocatalytic PCET method was applied to a broad‐scoped reduction of aryl ketones, unsaturated carbonyls, and aromatic compounds. The distinctive regioselectivities for the reduction of isoquinoline derivatives were found to occur on the carbon‐ring sides. PCET‐generated radical intermediate of quinoline could be trapped by alkene for proton relay‐assisted Minisci addition, forming the pharmaceutical aza ‐acenaphthene scaffold within one step. When using heteroatom(X)−H/C−H compounds as proton‐electron donors, this protocol could activate these inert bonds through photooxidative PCET to afford radicals and trap them by electron‐deficient unsaturated compounds, furnishing the direct X−H/C−H functionalization.