Direct Monofluoromethylthiolation with S‐(Fluoromethyl) Benzenesulfonothioate

Abstract

An electrophilic shelf-stable monofluoromethylthiolating reagent S-(fluoromethyl) benezenesulfonothioate (1) was developed. In the presence of a copper catalyst, reagent 1 coupled with a variety of aryl boronic acids to give the corresponding monofluoromethylthiolated arenes in high yields. In addition, addition of reagent 1 to alkyl alkenes in the presence of a silver catalyst gave alkyl monofluoromethylthioethers in high yields.

Thiosulfonates as Emerging Reactants: Synthesis and Applications

“…Inspired by the recent renewed interest in fluorinated thiosulfonates, the group of Chen developed the first approach towards S ‐(fluoromethyl) benzenethiosulfonate ( 74 ) via nucleophilic substitution of PhSO 2 SNa ( 51 ) with either CH 2 FI or CH 2 FCl in hazardous DMF as solvent (Scheme ) . If route 1 could be performed in another solvent, it would become attractive considering the low PMI RRC and PMI.…”

“…The group of Shen found that reactions of unactivated alkenes ( 240 ) with S ‐(difluoromethyl) benzenethiosulfonate ( 95 ) reactant occurred smoothly in the presence of silver nitrate as catalyst and potassium persulfate as stoichiometric oxidant (Scheme , route 1) . In addition, this methodology was also applied to introduce a monofluoromethylthio group onto sp 3 ‐hybridized carbon atoms via a reaction involving 240 under slightly modified conditions (route 2) . Xu and co‐workers developed an efficient intermolecular atom transfer thiosulfonylation of styrenes 265 via the combination of visible‐light photoredox and gold catalysis (route 3) .…”

Synthesis of Monofluoromethyl Selenoethers of Aryl and Alkyl from Organoselenocyanate via One‐Pot Reaction

“…Recently, fluoroalkyloxy groups including trifluoromethoxy (−OCF 3 ), difluoromethoxy (−OCF 2 H) groups and fluoroalkylthio groups, including trifluoromethylthio (−SCF 3 ), difluoromethylthio (−SCF 2 H), monofluoromethylthio (−SCFH 2 ) groups, have attracted considerable interests in both pharmaceutical industry and academia, mainly because of their high yet tunable lipophilicity that may dramatically improve the pharmacokinetic properties of a drug molecule . Accordingly, much attention is being devoted to the development of effective methods and reagents for their synthesis currently.…”

S‐(Diethyl phosphonodifluoromethyl)Benzenesulfonothioate: A New Reagent for the Synthesis of SCF2PO(OEt)2‐containing Molecules

“…Aiming at demonstrating further the synthetic potential of the reagent II, the difunctionalization of unactivated alkenes was studied. [11] After intensive investigations, the diethyl phosphonodifluoromethylthiolation sulfonylation of 6 was achieved leading to the corresponding product 7, although in a low yield (21%) despite all our efforts (Scheme 5). Nevertheless, the transformation was highly atom-economical and regioselective as 7 was obtained as a single regioisomer.…”