Activation of SFCF by the -Heterocyclic Carbene SIMes.

The greenhouse gas SFCF was photochemically activated with SIMes (1,3-Bis(2,4,6-trimethylphenyl)-4,5-dihydroimidazol-2-ylidene) to give 1,3-dimesityl-2,2-difluoroimidazolidine (SIMesF), and 1,3-dimesitylimidazolidine-2-sulfide, as well as the trifluoromethylated carbene derivative 1,3-dimesityl-2-fluoro-2-trifluoromethylimidazolidine. CF radicals, as well as SF, serve presumably as intermediates of the conversions. In addition, the photochemical activation of SFCF was performed in the presence of triphenylphosphine.

A 2,2-Difluoroimidazolidine Derivative for Deoxyfluorination Reactions: Mechanistic Insights by Experimental and Computational Studies.

A N-heterocyclic deoxyfluorinating agent SIMesF was synthesized by nucleophilic fluorination of N,N-1,3-dimesityl-2-chloroimidazolidinium chloride (3) at room temperature. SIMesF was applied to deoxyfluorinate carboxylic acids and alcohols and convert benzaldehyde into difluorotoluene. Mechanistic studies by NMR spectroscopy suggest reaction pathways of the carboxylic acid to acyl fluoride via outer-sphere fluorinations at an imidazolidinium ion by polyfluoride.

Reduction of SFCF iridium catalysis: radical trifluoromethylation of aromatics.

The greenhouse gas SFCF acts as CF source for the photocatalytic trifluoromethylation of arenes on using [Ir(dtbbpy)(ppy)]PF (4,4'-di--butyl-2,2'-dipyridyl, ppy = 2-phenylpyridine) as catalyst. The trifluoromethylation of CD in the presence of 1-octanol results in the concomitant generation of 1-fluorooctane, presumably by intermediate SF.

Access to β-Ketonitriles through Nickel-Catalyzed Carbonylative Coupling of α-Bromonitriles with Alkylzinc Reagents.

Herein, we report a nickel-catalyzed carbonylative coupling of α-bromonitriles and alkylzinc reagents with near stoichiometric carbon monoxide to give β-ketonitriles in good yields. The reaction is catalyzed by a readily available and stable nickel(II) pincer complex. The developed protocol tolerates substrates bearing a variety of functional groups, which would be problematic or incompatible with previous synthetic methods.