Catalytic C-O cleavage holds promise for the generation of commodity, value-added, and biologically relevant molecules from renewable biomass-derived feedstocks. Few well-defined systems are reported for selective secondary C-O cleavage using mild methods like hydrosilylation. Current state-of-the-art catalysts for secondary C-O cleavage lack selectivity necessary for applications in the reduction of complex substrates. An exploration of air-stable, cationic iridium bis(phosphine) catalysts has led to the development of a tunable manifold for secondary C-O cleavage on 5- and 6-membered carbocycles. We found that axial and equatorial methyl ethers show distinct reactivity profiles, leading to opportunities for catalyst-controlled selectivity in C-O reduction. Resting state analysis showed comparable speciation between catalysts with opposite reactivity, suggesting that selectivity is dictated by the electronic environment of the metal center. Applications in the selective deoxygenation of sterol derivatives have shown that our new catalysts are capable of mono-deoxygenation of complex polyethers.<br/>

Design of selective iridium bis(phosphine) catalysts for secondary C-O cleavage

Macromolecular Chemistry: The Second Century

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ACS Spring 2020 National Meeting & Expo

The official archive and repository for all ACS Meetings & Expositions abstracts and select posters or presentations.