Recent advances in cobalt-catalyzed allylic functionalization.

Unlike many other state-of-the-art transition-metal-catalyzed allylic substitutions, cobalt-catalyzed allylic substitution has received much less attention from synthetic chemists for a long time despite the fact that cobalt is an earth-abundant, low-cost and thus much more sustainable option as either a reagent or a catalyst in organic synthesis. Recently, there has been an upsurge in the use of cobalt catalysis in allylic functionalization reactions, including allylic substitution, nucleophilic allylation, and Heck-type allylic functionalization, to construct synthetically significant building blocks featuring a double bond available for diverse downstream synthetic manipulations. This review highlights the current development of cobalt catalysis in allylic functionalization with an in-depth discussion of the reaction scope and mechanistic insights.

Cobalt-Catalyzed Divergent Aminofluorination and Diamination of Styrenes with N-Fluorosulfonamides.

A cobalt-catalyzed aminofluorination reaction of styrenes with N-fluorosulfonamides serving as both the amination and fluorination agents has been developed. The switch of selectivity in this catalytic reaction from aminofluorination to diamination could be easily achieved by the addition of 1.0 equiv of PPh3. Both transformations tolerated a wide array of substrates under mild reaction conditions.

Cobalt fluorides: preparation, reactivity and applications in catalytic fluorination and C-F functionalization.

Recent advances in the investigation of cobalt fluorides in organofluorine chemistry are highlighted. The preparation and reactivity of inorganic and organometallic cobalt fluorides are discussed. The in-depth understanding of the structures and reactivity of cobalt fluorides allows chemists to develop diverse innovative catalytic fluorination and C-F functionalization.

Redox Neutral Radical-Relay Cobalt Catalysis toward C-H Fluorination and Amination.

A redox neutral radical-relay cobalt-catalyzed intramolecular C-H fluorination of N-fluoroamides featuring the in situ formed cobalt fluorides as the latent radical fluorinating agents is reported. Moreover, the reactivity of such a cobalt catalysis could be diverted from C-H fluorination to amination by engineering substrates' conformational flexibility. Preliminary mechanistic studies (UV-vis spectroscopy, cyclic voltammetry studies and DFT calculations, etc.) support the reaction proceeding a redox neutral radical-relay mechanism.