Cu(OAc)2-catalyzed remote benzylic C(sp3)–H oxyfunctionalization for CO formation directed by the hindered para-hydroxyl group with ambient air as the terminal oxidant under ligand- and additive-free conditions?

Green Chemistry Pub Date: 2013-10-11 DOI: 10.1039/C3GC41946K

Abstract

A hindered para-hydroxyl group-directed remote benzylic C(sp3)–H oxyfunctionalization has been developed for the straightforward transformation of 2,6-disubstituted 4-cresols, 4-alkylphenols, 4-hydroxybenzyl alcohols and 4-hydroxybenzyl alkyl ethers into various aromatic carbonyl compounds. The ligand- and additive-free Cu(OAc)2-catalyzed atmospheric oxidation mediated by ethylene glycol unlocks a facile, atom-economical, and environmentally benign C[double bond, length as m-dash]O formation for the functionalization of primary and secondary benzyl groups. Due to the pharmaceutical importance of 4-hydroxybenzaldehydes and 4-hydroxyphenones, the methodology is expected to be of significant value for both fundamental research and practical applications.

Graphical abstract: Cu(OAc)2-catalyzed remote benzylic C(sp3)–H oxyfunctionalization for C [[double bond, length as m-dash]] O formation directed by the hindered para-hydroxyl group with ambient air as the terminal oxidant under ligand- and additive-free conditions
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