A manganese-based catalyst system for general oxidation of unactivated olefins, alkanes, and alcohols

Non-noble metal-based catalyst systems consisting of inexpensive manganese salts, picolinic acid and various heterocycles enable epoxidation of the challenging (terminal) unactivated olefins, selective C-H oxidation of unactivated alkanes, and O-H oxidation of secondary alcohols with aqueous hydrogen peroxide. In the presence of the in situ generated optimal manganese catalyst, epoxides are generated with up to 81% yield from alkenes and ketone products with up to 51% yield from unactivated alkanes. This convenient protocol allows the formation of the desired products under ambient conditions (room temperature, 1 bar) by employing only a slight excess of hydrogen peroxide with 2,3-butadione as a sub-stoichiometric additive. An inexpensive MnCl 2 -picolinic acid catalyst with N-heterocyclic additives enables epoxidation of unactivated olefins, selective C-H oxidation of simple alkanes to ketones, and O-H oxidation of alcohols with hydrogen peroxide at ambient conditions.