CF₃SO₂X (X = Na, Cl) as reagents for trifluoromethylation, trifluoromethylsulfenyl-, -sulfinyl- and -sulfonylation and chlorination. Part 2: Use of CF₃SO₂Cl

Abstract

The recent progresses of the application of trifluoromethanesulfonyl chloride, CF3SO2Cl, in the formation of C–CF3, C–SCF3, C–SOCF3, and C–Cl bonds are summarised in this second part of a two-part review published back-to-back on both sodium trifluoromethanesulfinate, CF3SO2Na, (Part 1) and trifluoromethanesulfonyl chloride, CF3SO2Cl (Part 2). There are many reactions in common between these two reagents but it should be noted that CF3SO2Cl reacts under reductive conditions while CF3SO2Na requires oxidative conditions. Electrophilic chlorination is obviously the exclusive preserve of CF3SO2Cl that has been exploited with emphasis in enantioselective chlorination.

Fluoroalkylsulfonyl Chlorides Promoted Vicinal Chloro-fluoroalkylthiolation of Alkenes and Alkynes

“…CF 3 SO 2 Cl is a well-reported electrophilic trifluoro­methyl­thiolation reagent that generates reactive CF 3 SCl under reductive conditions . CF 3 SO 2 Cl has been used to generate CF 3 + for chloro-trifluoro­methylation of alkenes and alkynes (Scheme b) . We envisioned that CF 3 SO 2 Cl could be developed as a bifunctionalization reagent to introduce SCF 3 and chlorine groups without using an additional chlorine source (Scheme c).…”

Visible‐Light Photoredox‐Catalyzed Tandem Trifluoro‐methylation/Cyclization/Remote Oxidation of 1,6‐Dienes: Access to CF3‐Containing Five‐Membered Heterocycles

“…Trifluoromethylation of olefins has emerged as an efficient strategy for the preparation of CF 3 group‐containing molecules. A variety of trifluoromethylating agents have been developed and successfully employed, such as Togni reagents, [5a,7] Umemoto reagents, [8,9] Langlois reagent (CF 3 SO 2 Na), [10,11] Ruppert‐Prakash reagent (TMSCF 3 ), [12,13] trifluoromethane sulfonyl chloride, [14,15] trifluoromethyl iodide, [16] and the others [17]…”

Multiplex Chemical Labeling of Amino Acids for Protein Footprinting Structure Assessment

“…Chemical reagents and workflows that can produce multiple labels in a “one-pot synthesis” could help further advance HRPF toward being an accessible high-resolution structural biology technique. Toward this end, electrophilic and radical-mediated trifluoromethyl (TFM, −CF 3 ) labeling reagents may provide a simplified, uniform +CF 3 labeling (+68 Da) with an overall dynamic range of reactivity with side chains that permit “low reactivity” side chains to be more easily observed. ,− The •CF 3 radical is reactive with proteins but nominally stable in aqueous conditions and considered an appropriate complement to the •OH radical because of its pyramidal geometry, high electrophilicity, and high hydrophobicity. − The TFM group is an important synthetic motif in pharmaceuticals, agrochemicals, and specialty materials because CF 3 -substituted molecules often possess improved physical and chemical properties to lend stability to molecules in which they are introduced. , Thus, a wide range of interesting TFM reagents are available for research use. − Among these TFM reagents, a water soluble Langlois’ reagent (LR) is proven effective for the trifluoromethylation labeling of peptides and proteins via multiple redox initiation modes. ,− …”