Chemoselective Oxyfunctionalization of Functionalized Benzylic Compounds with a Manganese Catalyst

Whilst allowing for easy access to synthetically versatile motifs and for modification of bioactive molecules, the chemoselective benzylic oxidation reactions of functionalized alkyl arenes remain challenging. Reported in this study is a new non‐heme Mn catalyst stabilized by a bipiperidine‐based tetradentate ligand, which enables methylene oxidation of benzylic compounds by H(2)O(2), showing high activity and excellent chemoselectivity under mild conditions. The protocol tolerates an unprecedentedly wide range of functional groups, including carboxylic acid and derivatives, ketone, cyano, azide, acetate, sulfonate, alkyne, amino acid, and amine units, thus providing a low‐cost, more sustainable and robust pathway for the facile synthesis of ketones, increase of complexity of organic molecules, and late‐stage modification of drugs.