Site-selective C(sp3)–H oxidation of alkyl substrates devoid of functional handles

Abstract

Although the field of C(sp³)–H oxidation has progressed tremendously over the last decades, the selective oxidation of non-activated positions on hydrocarbon skeletons is still highly challenging. It usually requires the presence of a suitable functional handle in proximity to the desired oxidation site. Here, we present a novel approach to catalyst-directed C–H oxidation that relies on substrate binding via the solvophobic effect in fluorinated alcohols and thus is independent of specific functional groups on the substrate. The supramolecular catalyst Mn(mcp)-RS₂ enables the preferential oxidation at the fifth position from the less-hindered side on aliphatic substrates.