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A third generation of radical fluorinating agents based on N-fluoro-N-arylsulfonamides.

ABSTRACT: Radical fluorination has been known for a long time, but synthetic applications were severely limited by the hazardous nature of the first generation of reagents such as F₂ and the strongly electrophilic nature of the second generation of reagents such as N-fluorobenzenesulfonimide (NFSI) and Selecfluor^®. Here, we report the preparation, use and properties of N-fluoro-N-arylsulfonamides (NFASs), a class of fluorinating reagents suitable for radical fluorination under mild conditions. Their N-F bond dissociation energies (BDE) are 30-45?kJ?mol^-1 lower than the N-F BDE of the reagents of the second generation. This favors clean radical fluorination processes over undesired side reactions. The utility of NFASs is demonstrated by a metal-free radical hydrofluorination of alkenes including an efficient remote C-H fluorination via a 1,5-hydrogen atom transfer. NFASs have the potential to become the reagents of choice in many radical fluorination processes.

SUBMITTER: Meyer D

PROVIDER: S-EPMC6244228 | biostudies-literature | 2018 Nov

REPOSITORIES: biostudies-literature

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A third generation of radical fluorinating agents based on N-fluoro-N-arylsulfonamides.

Meyer Daniel D Jangra Harish H Walther Fabian F Zipse Hendrik H Renaud Philippe P

Nature communications 20181120 1

Radical fluorination has been known for a long time, but synthetic applications were severely limited by the hazardous nature of the first generation of reagents such as F<sub>2</sub> and the strongly electrophilic nature of the second generation of reagents such as N-fluorobenzenesulfonimide (NFSI) and Selecfluor<sup>®</sup>. Here, we report the preparation, use and properties of N-fluoro-N-arylsulfonamides (NFASs), a class of fluorinating reagents suitable for radical fluorination under mild c ...[more]

PMID: 30459353

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