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

• trifluoromethylsulfonylation reactions. We now focused this second part of the review on the similarly diverse uses of trifluoromethanesulfonyl chloride plus chlorination. This review appears in two parts that are published back-to-back. We encourage the readers to refer to Part 1 for a general introduction in the field [1

• trifluoromethanesulfonamide (triflamide) derivatives, which are used in drugs and agrochemicals [3]. The C-trifluoromethylsulfonylation is less reported than the corresponding O- and N-trifluoromethylsulfonylations, although the resulting triflone group is an important synthetic tool for further functionalisation [4][5

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

• 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

• ]. Since then, the use of CF3SO2Na has grown considerably for the creation of Csp3–CF3, Csp2–CF3 and Csp–CF3 bonds [17][18][19]. This reagent is also conveniently used in trifluoromethylsulfinylation and trifluoromethylsulfonylation reactions. More recently, from 2015, CF3SO2Na has found a new application

Synthesis of skeletally diverse alkaloid-like molecules: exploitation of metathesis substrates assembled from triplets of building blocks

• Sushil K. Maurya,
• Mark Dow,
• Stuart Warriner and
• Adam Nelson

Beilstein J. Org. Chem. 2013, 9, 775–785, doi:10.3762/bjoc.9.88

• ) and reaction with diisopropyl(3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-heptadecafluorodecyl)silyl (FDIPES) bromide, generated in situ from the corresponding silyl hydride, gave the fluorous-tagged building block 6b. Finally, desulfonylation (→ 19) and trifluoromethylsulfonylation yielded the alternative