4 years ago

Supramolecular recognition allows remote, site-selective C-H oxidation of methylenic sites in linear amines

Giorgio Olivo, Alessia Barbieri, Miquel Costas, Stefano Di Stefano, Giulio Farinelli, Osvaldo Lanzalunga
Site-selective C-H functionalization of aliphatic alkyl chains stands as a longstanding challenge in oxidation catalysis, given the comparable relative reactivity of the different methylenes. Herein, we describe a supramolecular, bioinspired approach to address this challenge. We decorated a manganese complex, able to catalyze C(sp3)-H hydroxylation with H2O2, with a supramolecular receptor (an 18-benzocrown-6 ether) that binds ammonium substrates via hydrogen bonding. Reversible pre-association of protonated primary aliphatic amines with the crown ether thus selectively exposes only remote positions (C8 and C9) to the oxidizing unit, yielding the site-selective oxidation and overriding the intrinsic reactivity of C-H bonds. Remarkably, the supramolecular control of the selectivity holds true for a whole series of linear amines, no matter the chain length and the presence of more (sterically) activated sites.

Publisher URL: http://onlinelibrary.wiley.com/resolve/doi

DOI: 10.1002/anie.201709280

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