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.

Highlights

  • We described the various uses of sodium trifluoromethanesulfinate in direct trifluoromethylation, trifluoromethylsulfenylation, trifluoromethylsufinylation and trifluoromethylsulfonylation reactions

  • We focused this second part of the review on the diverse uses of trifluoromethanesulfonyl chloride plus chlorination

  • In 2016, CF3SO2Cl was proposed for the first time as a new electrophilic trifluoromethylsulfenylation reagent by our research group [42]

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Summary

Introduction

We described the various uses of sodium trifluoromethanesulfinate in direct trifluoromethylation, trifluoromethylsulfenylation, trifluoromethylsufinylation and trifluoromethylsulfonylation reactions. We focused this second part of the review on the diverse uses of trifluoromethanesulfonyl chloride plus chlorination. The C-trifluoromethylsulfonylation is less reported than the corresponding O- and N-trifluoromethylsulfonylations, the resulting triflone group is an important synthetic tool for further functionalisation [4,5]. These sulfonylation reactions will not be further detailed hereafter. The direct introduction of CF3S and CF3S(O) motifs occupies a prime position in this review

Trifluoromethylation
Trifluoromethylsulfenylation
Trifluoromethylsulfinylation
Chlorination
Conclusion
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