Direct electrophilic N-trifluoromethylthiolation of amines with trifluoromethanesulfenamide

Abstract

SummaryThe CF3SN moiety is a substituent with interesting properties. However, there is no easy synthetic access to molecules bearing this group. The trifluoromethanesulfenamide is a new reagent for the electrophilic trifluoromethylthiolation which reacts easily with amines to obtain trifluoromethylsulfanylamines with good yields.

First and second generation of trifluoromethanesulfenamide reagent: A trifluoromethylthiolating comparison

“…The crude residue was purified by flash chromatography to afford the desired product. In accordance with literature [36]. In accordance with literature [36].…”

“…Finally, trans-amination reactions to access to other trifluoromethanesulfenamides (14) have been envisaged (Scheme 1) [36].…”

“…One of the first developed reagents was the 1st generation of trifluoromethanesulfenamide 1 [25,[32][33][34][35][36]. Recently, the 2nd generation of trifluoromethanesulfenamide 2 has been introduced to realize more difficult reactions [29,37,38] (Fig.…”

Selective trifluoromethylthiolation of heteroaromatic sp2 C–H bonds with the 2nd generation of trifluoromethanesulfenamide reagent

“…Previously, we have described a new efficient reagent for electrophilic trifluoromethylthiolation, namely the N-methyl-Nphenyl trifluoromethanesulfenamide (1a) [25,[31][32][33][34], which could react with organometallic species [31,33]. More recently, a 2nd generation of reagent, namely the N-methyl-N-tosyl trifluoromethanesulfenamide (1b), has been introduced and has shown a higher reactivity [35] (Fig.…”

Electrophilic trifluoromethylthiolation of thiols with trifluoromethanesulfenamide

“…The recent progress was initiated by the work of Billard, Langlois and coworkers when they published a synthesis of PhNHSCF 3 1 and its derivatives. 22 These compounds are easyto-handle electrophilic SCF 3 reagents that can react with alkenes and alkynes, 23 indoles, 24 organometallic species, 25 tryptamines, 26 amines, 27 allyl silanes 28 and phenols. 29 An interesting cyclization was observed with different internal alkynes and PhNHSCF 3 furnishing the corresponding triuoromethylthio substituted indoles, 30 benzofurans and benzothiophenes, 31 1H-isochromen-1-ones, 32 2H-benzo[e][1,2]thiazine 1,1-dioxides 33 and benzofulvenes.…”