Deprotection of benzyl ethers via solvent anion-mediated EDA complex.

Benzyl ethers are among the most robust and indispensable protecting groups in the synthesis of complex natural products and pharmaceuticals, providing effective neutralization of the reactive hydroxy group in phenols and alcohols. However, their cleavage necessitates the use of expensive catalysts, hazardous conditions, or excessive organic additives. Herein, we report a catalyst-free, photoinduced debenzylation protocol of phenolic and aliphatic ethers. By leveraging in situ generated solvent-anions as the reductant, the protocol achieves chemoselective debenzylation in the presence of alkenes, amides, carbamates, alcohols, and boronic esters in high yields under mild conditions. This strategy circumvents the need for costly hydrogenation catalysts or toxic reagents, providing a sustainable and economically viable alternative for debenzylation.