Intramolecular C(sp3)–H Bond Oxygenation by Transition-Metal Acylnitrenoids

Article abstract of DOI:10.1002/anie.202009335

This study demonstrates for the first time that easily accessible transition-metal acylnitrenoids can be used for controlled direct C(sp³)-H oxygenations. Specifically, a ruthenium catalyst activates N-benzoyloxycarbamates as nitrene precursors towards regioselective intramolecular C?H oxygenations to provide cyclic carbonates, hydroxylated carbamates, or 1,2-diols. The method can be applied to the chemoselective C?H oxygenation of benzylic, allylic, and propargylic C(sp³)?H bonds. The reaction can be performed in an enantioselective fashion and switched in a catalyst-controlled fashion between C?H oxygenation and C?H amination. This work provides a new reaction mode for the regiocontrolled and stereocontrolled conversion of C(sp³)-H into C(sp³)?O bonds.