Copper-oxygen adducts: new trends in characterization and properties towards C−H activation.

J. De Tovar, R. Leblay, Y. Wang, L. Wojcik, A. Thibon-Pourret, M. Reglier,* A. J. Simaan,* N. Le Poul,* C. Belle,* Chem. Sci. 2024, in press, DOI: 10.1039/D4SC01762E

This review summarizes the latest discoveries in the field of C−H activation by copper monoxygenases and more particularly
by their bioinspired systems. This work first describes recent background on copper-containing enzymes along with
additional interpretations about the nature of the active copper-oxygen intermediates. It then focuses on relevant examples
of bioinorganic synthetic copper-oxygen intermediates according to their nuclearity (mono to polynuclear). This includes a
detailed description of the spectroscopic features of these adducts as well as their reactivity towards the oxidation of
recalcitrant Csp3 − H bonds. The last part is devoted to the significant expansion of heterogeneous catalytic systems based
on copper-oxygen cores (i.e. within zeolites frameworks)