Intramolecular C(sp3)–H Bond Oxygenation by Transition‐Metal Acylnitrenoids. (24th September 2020)

• Record Type: Journal Article
• Authors: Tan, Yuqi; Chen, Shuming; Zhou, Zijun; Hong, Yubiao; Ivlev, Sergei; Houk, K. N.; Meggers, Eric
• Is Part Of: Angewandte Chemie. Volume 132:Number 48(2020)
• Page Start: 21890
• Page End: 21894
• Publication Date: 2020-09-24
• Subjects: C−H functionalization -- enantioselectivity -- nitrenoids -- oxygenation -- ruthenium; Chemistry -- Periodicals; 540
• DOI: 10.1002/ange.202009335
• Languages: English
• ISSNs: 0044-8249

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. Abstract : Transition‐metal nitrenoids are well‐established for their C−H amination chemistry but this work demonstrates that N‐acylnitrenoids can surprisingly undergo C(sp 3 )–H oxygenations instead, even in an enantioselective fashion.