Intramolecular C(sp3 )-H Bond Oxygenation by Transition-Metal Acylnitrenoids
Yuqi Tan1, Shuming Chen2, Zijun Zhou1
1Fachbereich Chemie, Philipps-Universität Marburg, Hans-Meerwein-Straße 4, 35043, Marburg, Germany.
Abstract:
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.
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