Synthesis, Characterization, and Stereoselective Oxidations of the Dinuclear Copper(II) Complex Derived from a Chiral Diamino-m-xylenetetra(benzimidazole) Ligand

Article abstract of DOI:10.1002/ejic.201500046

Recent advances in dinuclear copper complexes as mimics of the catalytic centers of tyrosinase and catechol oxidase allowed the reproduction of the structural and mechanistic aspects of the enzymes. However, a challenging objective is the development of chiral complexes for bioinspired enantioselective oxidation reactions. Here, we report the synthesis and characterization of a dinuclear copper(II) complex with a new chiral diamino-m-xylenetetra(benzimidazole) ligand (L55Bu4), which has chiral centers at the four 2-methylbutyl substituents of the benzimidazole rings. The spectral characteristics, ligand binding properties, and reactivity of [Cu^II₂L55Bu4]⁴⁺ in the catalytic oxidations of several biogenic catechols (L-/D-dopa, L-/D-DopaOMe, and L-/D-norepinephrine) and thioanisole are reported. The best discriminating properties are displayed towards the DopaOMe derivatives, for which the oxidation rate of the L enantiomer is approximately one order of magnitude larger than that of the opposite D isomer. A dinuclear copper(II) complex derived from a chiral hexadentate nitrogen ligand is reported as a new catalyst for asymmetric oxidations. For biogenic catechols as model substrates, the best enantioselectivity is obtained in the oxidation of the methyl esters of L-/D-Dopa, for which 70%ee is obtained in favor of the L enantiomer.