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Copper-catalyzed remote C(sp3)-H azidation and oxidative trifluoromethylation of benzohydrazides.


ABSTRACT: The Hofmann-Löffler-Freytag (HLF) reaction is a prototypical example of radical-based remote functionalization of unactivated C(sp3)-H bond. While 1,5-hydrogen atom transfer (1,5-HAT) of the amidyl radical is thermodynamically favorable and is well-established, the method for the subsequent functionalization of the translocated carbon radical is still limited. We report herein two catalytic remote C(sp3)-H functionalization protocols. Cu(MeCN)4PF6-catalyzed reaction of 2-alkyl benzohydrazides 3 with TMSN3 in the presence of MeCO2OtBu affords the ?-azido amides 4, while CuCl-catalyzed reaction of 3 with Togni's reagent provides 2-(?-trifluoromethylvinyl)benzamides 5 via an oxidative ?-trifluoromethylation of the alkyl group. Mechanistic studies suggest that the ?-azidation of benzohydrazides 3 goes through 1,5-HAT followed by a Cu-mediated azido transfer cascade, while the oxidative ?-trifluoromethylation of 3 proceeds via, after 1,5-HAT process, a radical-polar crossover mechanism.

SUBMITTER: Bao X 

PROVIDER: S-EPMC6377619 | biostudies-literature | 2019 Feb

REPOSITORIES: biostudies-literature

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Copper-catalyzed remote C(sp<sup>3</sup>)-H azidation and oxidative trifluoromethylation of benzohydrazides.

Bao Xu X   Wang Qian Q   Zhu Jieping J  

Nature communications 20190215 1


The Hofmann-Löffler-Freytag (HLF) reaction is a prototypical example of radical-based remote functionalization of unactivated C(sp<sup>3</sup>)-H bond. While 1,5-hydrogen atom transfer (1,5-HAT) of the amidyl radical is thermodynamically favorable and is well-established, the method for the subsequent functionalization of the translocated carbon radical is still limited. We report herein two catalytic remote C(sp<sup>3</sup>)-H functionalization protocols. Cu(MeCN)<sub>4</sub>PF<sub>6</sub>-cata  ...[more]

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