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-methylbutylsubstituents of the benzimidazole rings. The spectral characteristics, ligand binding properties, and reactivity of [CuII 2L55Bu4]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.
Synthesis, Characterization, and Stereoselective Oxidations of the Dinuclear Copper(II) Complex Derived from a Chiral Diamino-m-xylenetetra(benzimidazole) Ligand
PERRONE, MARIA LUCIA;LO PRESTI, ELIANA;DELL'ACQUA, SIMONE;MONZANI, ENRICO;CASELLA, LUIGI
2015-01-01
Abstract
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-methylbutylsubstituents of the benzimidazole rings. The spectral characteristics, ligand binding properties, and reactivity of [CuII 2L55Bu4]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.I documenti in IRIS sono protetti da copyright e tutti i diritti sono riservati, salvo diversa indicazione.
