Intramolecular C(sp<sup>3</sup>)–H Bond Oxygenation by Transition‐Metal Acylnitrenoids
Yuqi Tan, Shuming Chen, Zijun Zhou, Yubiao Hong, Sergei I. Ivlev, K. N. Houk, Eric Meggers
Abstract
Abstract 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.