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

Yuqi Tan; Shuming Chen; Zijun Zhou; Yubiao Hong; Sergei Ivlev; K N Houk; Eric Meggers

doi:10.1002/anie.202009335

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

Angew Chem Int Ed Engl. 2020 Nov 23;59(48):21706-21710. doi: 10.1002/anie.202009335. Epub 2020 Sep 24.

Authors

Yuqi Tan¹, Shuming Chen², Zijun Zhou¹, Yubiao Hong¹, Sergei Ivlev¹, K N Houk², Eric Meggers¹

Affiliations

¹ Fachbereich Chemie, Philipps-Universität Marburg, Hans-Meerwein-Straße 4, 35043, Marburg, Germany.
² Department of Chemistry and Biochemistry, University of California, Los Angeles, CA, 90095-1569, USA.

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.

Keywords: C−H functionalization; enantioselectivity; nitrenoids; oxygenation; ruthenium.

Publication types

Research Support, Non-U.S. Gov't