Catalytic C-O cleavage via hydrosilylation holds promise for the generation of value-added, and biologically relevant molecules from renewable biomass-derived feedstocks. 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.<br/>

Role of catalyst structure and substrate conformation in iridium-catalyzed ether cleavage

ACS Fall 2020 Virtual Meeting

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