Ricerc@Sapienza

Herein we report that an imine-based iron complex decorated with crown-ether moieties self-assembles in CH3CN solution from three building blocks (namely Fe(CH3CN)2(OTf)2, 2-picolylamine and aldehyde 6a) added in the proper molar ratio (1:2:2, respectively). Aldehyde 6a, endowed with a benzocrown-ether receptor, can be prepared in two steps from commercial materials with high yields (79 %) and no need of chromatographic separations. The self-assembled complex is highly stable in CH3CN solution.

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 3 )-H hydroxylation with H 2 O 2 is equipped with 18-benzocrown-6 ether receptors that bind ammonium substrates via hydrogen bonding.