%0 Journal Article
%T Cupric-superoxide complex that induces a catalytic aldol reaction-type C¨CC bond formation
%J -
%D 2019
%R https://doi.org/10.1038/s42004-019-0115-6
%X Much recent attention has been focused on the structure and reactivity of transition-metal superoxide complexes, among which mononuclear copper(II)-superoxide complexes are recognized as key reactive intermediates in many biological and abiological dioxygen-activation processes. So far, several types of copper(II)-superoxide complexes have been developed and their electrophilic reactivity has been explored in C¨CH and O¨CH bond activation reactions. Here we demonstrate that a mononuclear copper(II)-(end-on)superoxide complex supported by a N-[(2-pyridyl)methyl]-1,5-diazacyclooctane tridentate ligand can induce catalytic C¨CC bond formation reaction between carbonyl compounds (substrate) and the solvent molecule (acetone), giving ¦Â-hydroxy-ketones (aldol). Kinetic and spectroscopic studies at low temperature as well as DFT calculation studies support a nucleophilic reactivity of the superoxide species toward the carbonyl compounds, providing new insights into the reactivity of transition-metal superoxide species not only in biological oxidation reactions but also in synthetic organic chemistry
%U https://www.nature.com/articles/s42004-019-0115-6