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A novel synthetic protocol for the direct oxidation of alkanes, including cyclic and linear ones, to give ketones and alcohols using hydrogen peroxide as terminal oxidant under ambient conditions is presented. The active catalyst for this challenging transformation is conveniently generated by combination of simple Fe salts with N‐methyl bis(picolylamine) (Me‐bpa). Utilizing picolinic acid as additive leads to improved yields of ketones and alcohols (32‐57 %). The reaction can be conveniently scaled up to multi‐g scale. [ABSTRACT FROM AUTHOR]