An atom-economical method for radical (phenylsulfonyl)difluoromethylation of isocyanides with PhSOCFH under transition-metal-free conditions has been developed. A PhSOCF radical is generated through the oxidation of PhSOCF after the deprotonation of PhSOCFH in one pot. The reaction exhibits excellent functional-group tolerance and the resulting products can be further modified with the removal of a PhSO group to give other CF-containing compounds.
A pentacoordinate bis(difluoromethyl)silicate anion, [Me3 Si(CF2 H)2 ](-) , is observed for the first time by the activation of Me3 SiCF2 H with a nucleophilic alkali-metal salt and 18-crown-6. Further study on its reactivity by tuning the countercation effect led to the discovery and development of an efficient, catalytic nucleophilic difluoromethylation of enolizable ketones with Me3 SiCF2 H by using a combination of CsF and 18-crown-6 as the initiation system. Mechanistic investigations demonstrate that [(18-crown-6)Cs](+) [Me3 Si(CF2 H)2 ](-) is a key intermediate in this catalytic reaction.
scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.