Synthesis of Trifluoromethanesulfinamidines and -sulfanylamides

Abstract

Fluorinated moieties constitute important substituents used in many applications to modify the properties of molecules. The action of DAST onto Ruppert's reagent yields to a not isolable intermediate that can then react with various primary amines to give trifluoromethanesulfinamidines and trifluoromethanesulfanylamides. Such compounds were unknown until now and constitute interesting new families of fluorinated molecules.

Direct electrophilic N-trifluoromethylthiolation of amines with trifluoromethanesulfenamide

“…Several years ago, we have described an easy access to trifluoromethanesulfenamides [36], starting from DAST, Ruppert reagent, and primary amines [37]. However, even though this strategy gave good results with primary amines, secondary amines do not react under these conditions, thus limiting the access to a large panel of trifluoromethylsulfanylamines.…”

Electrophilic Trifluoromethanesulfanylation of Organometallic Species with Trifluoromethanesulfanamides

“…Furthermore, the possibility of extending this reaction to more fluorinated reagent has been verified. Grignard reagent 2 c reacts with pentafluoromethanesulfanamide 1 b [14] to give the corresponding pentafluoroethylthioether 9 in satisfactory yield (Scheme 2). This result suggests that 1 b and 1 a are similarly reactive.…”

“…[14] These reagents have already demonstrated their potential in the electrophilic trifluoromethanesulfanylations of alkenes, alkynes,…”

BrØsted acid-catalyzed electrophilic trifluoromethylthiolation of indoles using thermally stable trifluoromethylthiolating reagent

“…The trifluoromethylthiolated arenes or heteroarenes could be accessed easily by a transition metal-catalyzed cross-coupling reaction of an aryl halide with a nucleophilic trifluoromethylthio reagent such as AgSCF 3 , Me 4 NSCF 3 or with sulfur and TMSCF 3 as the trifluoromethylthio source [4]. Alternatively, direct coupling of nucleophilic aryl boronic acid with an electrophilic trifluoromethylthiolating reagent could afford the desired trifluoromethylthiolated arene or heteroarene [5]. In this regard, in recent years, there have been considerable efforts in the direct trifluoromethylthiolation of indoles.…”