Intramolecular C(sp ³ )–H Bond Oxygenation by Transition‐Metal Acylnitrenoids

This study demonstrates for the first time that easily accessible transition‐metal acylnitrenoids can be used for controlled direct C(sp 3 )‐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(sp 3 )−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(sp 3 )‐H into C(sp 3 )−O bonds.