Computational Insights of Selective Intramolecular O-atom Transfer Mediated by Bioinspired Copper Complexes.

ABSTRACT: The stereoselective copper-mediated hydroxylation of intramolecular C-H bonds from tridentate ligands is reinvestigated using DFT calculations. The computational study aims at deciphering the mechanism of C-H hydroxylation obtained after reaction of Cu(I) precursors with dioxygen, using ligands bearing either activated (L¹ ) or non-activated (L² ) C-H bonds. Configurational analysis allows rationalization of the experimentally observed regio- and stereoselectivity. The computed mechanism involves the formation of a side-on peroxide species (P) in equilibrium with the key intermediate bis-(μ-oxo) isomer (O) responsible for the C-H activation step. The P/O equilibrium yields the same activation barrier for the two complexes. However, the main difference between the two

SUBMITTER: Gamboa-Ramirez S 

PROVIDER: S-EPMC9828472 | biostudies-literature | 2022 Nov

REPOSITORIES: biostudies-literature