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

• Hélène Chachignon,
• Hélène Guyon and
• Dominique Cahard

Beilstein J. Org. Chem. 2017, 13, 2800–2818, doi:10.3762/bjoc.13.273

• ; trifluoromethylation; trifluoromethylsulfenylation; trifluoromethylsufinylation; trifluoromethylsulfonylation; Introduction In the preceding paper, we described the various uses of sodium trifluoromethanesulfinate in direct trifluoromethylation, trifluoromethylsulfenylation, trifluoromethylsufinylation and

• . Terminal alkynes could also be submitted to these conditions successfully, albeit in lower yields. 2 Trifluoromethylsulfenylation In 2016, CF3SO2Cl was proposed for the first time as a new electrophilic trifluoromethylsulfenylation reagent by our research group [42]. To achieve that kind of transformation

• -trifluoromethylsulfenylation did not occur with 3-substituted substrates. Other azaarenes, such as pyrrole derivatives, as well as enamines or silyl enol ethers were also compatible with these conditions, and furnished the corresponding products in moderate to good yields. The key step of the reaction comprises the formation

CF₃SO₂X (X = Na, Cl) as reagents for trifluoromethylation, trifluoromethylsulfenyl-, -sulfinyl- and -sulfonylation. Part 1: Use of CF₃SO₂Na

• Hélène Guyon,
• Hélène Chachignon and
• Dominique Cahard

Beilstein J. Org. Chem. 2017, 13, 2764–2799, doi:10.3762/bjoc.13.272

• 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. Keywords: fluorine; sulfur; trifluoromethylation; trifluoromethylsulfenylation; trifluoromethylsulfonylation

• atom is retained for trifluoromethylsulfenylation (also named trifluoromethylthiolation), trifluoromethylsulfinylation, or trifluoromethylsulfonylation reactions. Typically, CF3SO2Na reacts under oxidative conditions whereas CF3SO2Cl requires reductive conditions. The advent of a new dynamism and the