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. 2023 Aug 28;62(35):e202308048.
doi: 10.1002/anie.202308048. Epub 2023 Jul 19.

Cobalt-Catalyzed Wagner-Meerwein Rearrangements with Concomitant Nucleophilic Hydrofluorination

Reece H Hoogesteger  1 , Nicola Murdoch  1 , David B Cordes  1 , Craig P Johnston  1
Affiliations

Cobalt-Catalyzed Wagner-Meerwein Rearrangements with Concomitant Nucleophilic Hydrofluorination

Reece H Hoogesteger et al. Angew Chem Int Ed Engl. .

Abstract

We report a cobalt-catalyzed Wagner-Meerwein rearrangement of gem-disubstituted allylarenes that generates fluoroalkane products with isolated yields up to 84 %. Modification of the counteranion of the N-fluoropyridinium oxidant suggests the substrates undergo nucleophilic fluorination during the reaction. Subjecting the substrates to other known metal-mediated hydrofluorination procedures did not lead to observable 1,2-aryl migration. Thus, indicating the unique ability of these cobalt-catalyzed conditions to generate a sufficiently reactive electrophilic intermediate capable of promoting this Wagner-Meerwein rearrangement.

Keywords: Cations; Cobalt Catalysis; Hydrofluorination; Phenonium Ion; Wagner-Meerwein.

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