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. 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.

Supramolecular recognition allows remote, site-selective C-H oxidation of methylenic sites in linear amines / Olivo, Giorgio; Farinelli, Giulio; Barbieri, Alessia; Lanzalunga, Osvaldo; Di Stefano, Stefano; Costas, Miquel. - In: ANGEWANDTE CHEMIE. INTERNATIONAL EDITION. - ISSN 1433-7851. - STAMPA. - 56:51(2017), pp. 16347-16351. [10.1002/anie.201709280]

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

Olivo, Giorgio
;
FARINELLI, GIULIO;Barbieri, Alessia;Lanzalunga, Osvaldo;Di Stefano, Stefano
;
2017

Abstract

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. 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.
2017
bioinspired catalysis; C-H oxidation; molecular recognition; regioselectivity; supramolecular chemistry; catalysis; chemistry (all)
01 Pubblicazione su rivista::01a Articolo in rivista
Supramolecular recognition allows remote, site-selective C-H oxidation of methylenic sites in linear amines / Olivo, Giorgio; Farinelli, Giulio; Barbieri, Alessia; Lanzalunga, Osvaldo; Di Stefano, Stefano; Costas, Miquel. - In: ANGEWANDTE CHEMIE. INTERNATIONAL EDITION. - ISSN 1433-7851. - STAMPA. - 56:51(2017), pp. 16347-16351. [10.1002/anie.201709280]
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Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/11573/1052514
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