Remote Amino Acid Recognition Enables Effective Hydrogen Peroxide Activation at a Manganese Oxidation Catalyst.

ABSTRACT: Precise delivery of a proton plays a key role in O₂ activation at iron oxygenases, enabling the crucial O-O cleavage step that generates the oxidizing high-valent metal-oxo species. Such a proton is delivered by acidic residues that may either directly bind the iron center or lie in its second coordination sphere. Herein, a supramolecular strategy for enzyme-like H₂ O₂ activation at a biologically inspired manganese catalyst, with a nearly stoichiometric amount (1-1.5 equiv) of a carboxylic acid is disclosed. Key for this strategy is the incorporation of an α,ω-amino acid in the second coordination sphere of a chiral catalyst via remote ammonium-crown ether recognition. The properly positioned carboxylic acid function enables effective activation of hydroge

SUBMITTER: Vicens L 

PROVIDER: S-EPMC9304166 | biostudies-literature | 2022 Feb

REPOSITORIES: biostudies-literature