Beschreibung:
<jats:title>Abstract</jats:title><jats:p>Site‐selective C−H functionalization of aliphatic alkyl chains is a longstanding challenge in oxidation catalysis, given the comparable relative reactivity of the different methylenes. A supramolecular, bioinspired approach is described to address this challenge. A Mn complex able to catalyze C(sp<jats:sup>3</jats:sup>)‐H hydroxylation with H<jats:sub>2</jats:sub>O<jats:sub>2</jats:sub> is equipped with 18‐benzocrown‐6 ether receptors that bind ammonium substrates via hydrogen bonding. Reversible pre‐association of protonated primary aliphatic amines with the crown ether selectively exposes remote positions (C8 and C9) to the oxidizing unit, resulting in a site‐selective oxidation. Remarkably, such control of selectivity retains its efficiency for a whole series of linear amines, overriding the intrinsic reactivity of C−H bonds, no matter the chain length.</jats:p>