Abstract
Sodium trifluoromethanesulfinate, CF3SO2Na, and trifluoromethanesulfonyl chloride, CF3SO2Cl, are two popular reagents that are widely used for the direct trifluoromethylation of a large range of substrates. Further, these two reagents are employed for the direct trifluoromethylsulfenylation and trifluoromethylsulfinylation, the introduction of the SCF3 and the S(O)CF3 group, respectively. In addition to the aforementioned reactions, the versatility of these two reagents is presented in other reactions such as sulfonylation and chlorination. This first part is dedicated to sodium trifluoromethanesulfinate.
Highlights
In organofluorine chemistry, the CF3 group occupies a place of choice as privileged structural motif in the development of multifaceted catalysts and ligands for organic synthesis as well as in the design of pharmaceuticals, agrochemicals and specialty materials [1,2,3,4]
Csp3–CF3 bond-forming reactions Synthesis of α-trifluoromethyl ketones from alkenes: After their original reports on the trifluoromethylation of aromatics [16] and disulfides (Scheme 69) [20], Langlois and co-workers demonstrated that enol acetates 1a–c were converted into the corresponding α-trifluoromethyl ketones upon treatment with CF3SO2Na with tertbutyl hydroperoxide (TBHP) and a catalytic amount of copper(II) triflate (Scheme 1) [21]
Hydrotrifluoromethylation of alkenes: Direct alkene hydrotrifluoromethylation by means of CF3SO2K under electrochemical oxidation was first reported by Tommasino and co-workers in 2002 on three alkenes but yields were below 20% due to the formation of oxidised byproducts [38]
Summary
The CF3 group occupies a place of choice as privileged structural motif in the development of multifaceted catalysts and ligands for organic synthesis as well as in the design of pharmaceuticals, agrochemicals and specialty materials [1,2,3,4]. The CF3O group is of high interest but difficulties still exist to introduce this motif directly onto organic molecules [8] The reasons behind such massive interest for the CF3 group are due to the specific physical and chemical properties of the compounds that contain it. (4.0 versus 3.5 on the Pauling scale) and its hydrophobicity is large (0 for H, 0.51 for Me, and 1.07 for CF3) [10] In this respect, judicious installation of CF3 group(s) in catalysts or ligands is an effective tool to tune their reactivity and selectivity in synthesis. The use of CF3SO2Na has grown considerably for the creation of Csp3–CF3, Csp2–CF3 and Csp–CF3 bonds [1719] This reagent is conveniently used in trifluoromethylsulfinylation and trifluoromethylsulfonylation reactions. From 2015, CF3SO2Na has found a new application as source of SCF3 for direct trifluoromethylsulfenylation
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