Cobalt‐Catalyzed Wagner–Meerwein Rearrangements with Concomitant Nucleophilic Hydrofluorination

Abstract

AbstractWe 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.