Oxidative Cleavage of Glycosidic Bonds by Synthetic Mimics of Lytic Polysaccharide Monooxygenases.

Lytic polysaccharide monooxygenases (LPMOs) cleave polysaccharides through copper-bound oxyl radicals. We report a synthetic mimic of LPMO that uses micelle-stabilized hydrogen bonds to bind a glycan and two molecularly imprinted hydrophobic pockets to accommodate the alkyl tail of the glycoside and a copper cofactor, respectively. Cleavage of alkyl glycosides and oligosaccharides with hydrogen peroxide occurs at room temperature in aqueous solution, with selectivities for both the glycan and the alkyl aglycon.