Na₂S·9H₂O Enabled Defluorodisulfuration and Hydrodefluorination of Perfluorobutyl Tetralones: Synthesis of Trifluoromethyl 1,2-Dithioles

Abstract

An unprecedented defluorocyclization of perfluorobutyl tetralones with Na 2 S•9H 2 O was developed for the synthesis of trifluoromethyl 1,2-dithioles, which provided chemists novel access to biologically and pharmaceutically relevant organofluorides. Successive C(sp 3 )−F bond functionalization at the perfluoroalkyl chain is vital for the formation of four C−H/C−S/ S−S bonds and a five-membered S-heterocycle assembly. Cheap, weakly toxic, and odorless inorganic sulfide Na 2 S•9H 2 O acts as both a disulfurating precursor and a hydrodefluorinating reagent in this tandem multi-bond-interconverting reaction.

“On-water” defluorophosphorylation of trifluoromethylated enones with phosphine oxides

“…18 However, the influence of distinctive fluorine effects on “on-water” chemistry remains less explored. 19 Continuing with our research interests on C–F bond functionalization and sustainable chemistry, 20 herein we have made efforts to establish a simpler and more efficient defluorinative process in aqueous medium for rapidly accessing functionalized gem -difluorodienes.…”