Selective C–O bond cleavage at benzylic positions enabled by Zirconocene and Photoredox catalysis

We have developed a catalytic protocol for the selective cleavage of C–O bonds at benzylic positions using zirconocene and photoredox catalysis. This catalytic system enables the reductive cleavage of C–O bonds in both benzyl ethers and benzyl alcohols. Additionally, aromatic carbonyl compounds undergo deoxygenation to afford the corresponding hydrogenated products. Mechanistic studies support that ZrIII is the catalytically active species responsible for the C–O bond cleavage, driven by the formation of a strong Zr–O bond. To create your abstract, type over the instructions in the template box below. Fonts or abstract dimensions should not be changed or altered. • Zirconocene and photoredox catalysis enable C–O bond cleavage of unstrained benzyl ethers. • Benzyl alcohols, ethers, and aromatic carbonyls undergo reductive deoxygenation. • Mechanistic studies support the involvement of Zr(III) and a radical pathway.