Organophotoredox-Catalyzed Chemoselective Deprotection for Phenolic Ethers Driven by the Oxophilicity of Silicon

An organophotocatalyzed approach for the chemoselective dealkylation of phenols is developed. This method demonstrates exceptional selectivity toward the cleavage of phenolic ethers over equivalent aliphatic ethers and alkyl benzoates, presenting a broad range of functional group sustainability. This strategy also enables selective debenzylation of phenols in the presence of reduction-sensitive functional groups. Mechanistic studies and photophysical experiments provide evidence for the selective disintegration of C-O bonds through photo-oxidation, facilitated by the oxophilicity of silicon.