Decoding the Mechanism of Intramolecular Cu-Directed Hydroxylation of sp³ C-H Bonds.

ABSTRACT: The use of copper in directed C-H oxidation has been relatively underexplored. In a seminal example, Schönecker showed that copper and O₂ promoted the hydroxylation of steroid-containing ligands. Recently, Baran (J. Am. Chem. Soc. 2015, 137, 13776) improved the reaction conditions to oxidize similar substrates with excellent yields. In both reports, the involvement of Cu₂O₂ intermediates was suggested. In this collaborative article, we studied the hydroxylation mechanism in great detail, resulting in the overhaul of the previously accepted mechanism and the development of improved reaction conditions. Extensive experimental evidence (spectroscopic characterization, kinetic analysis, intermolecular reactivity, and radical trap experiments) is provided to sup

SUBMITTER: Trammell R 

PROVIDER: S-EPMC5792191 | biostudies-literature | 2017 Aug

REPOSITORIES: biostudies-literature