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.

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.

A new class of chiral 1,2-amino ether ligands, readily accessible from naturally occurring α-amino- or α-hydroxy acids, was found to provide high levels of both conversion and stereocontrol (up to 95:5 er) in intramolecular carbolithiation reactions, outperforming the benchmark ligand (-)-sparteine. The ligand could be used in a substoichiometric amount (0.25 equiv) without significant loss of enantioselectivity.

A metal‐free protocol for the domino trifluoromethylthiolation/decarboxylation of β‐ketocarboxylic acids is described. The catalytic reactions take place in acetonitrile in the presence of aqueous ammonium hydroxide and N‐trifluoromethylthiosaccharin. The sequence of events and reaction mechanism were established experimentally and using density functional theory calculations. This synthetic method offers a convenient alternative to known routes for the synthesis of α‐trifluoromethylthio‐substituted ketones.