Visible light mediated C–H trifluoromethylation of (hetero)arenes

Abstract

A protocol on visible light mediated C-H trifluoromethylation of unactivated (hetero)arenes under blue LED irradiation has been developed. The reaction enables the rapid construction of a range of CF3-containing (hetero)arenes...

Recent advances in transition metal-mediated trifluoromethylation reactions

“…In 2022, Xiao and co-worker disclosed a photomediated strategy for C(sp 2 )–H trifluoromethylation of unactivated (hetero)arenes (Scheme 66). 127 Xiao's group employed a readily available trifluoromethylsulfonyl–pyridinium salt (TFSP) as the CF 3 source in the presence of photocatalyst, Ir(ppy) 3 . Of note, the protocol was well compatible with a wide variety of arenes and N, O, and S containing hetero arenes affording moderate to good yields of the desired products.…”

Direct Perfluoroalkylation of C−H Bonds in (Hetero)arenes

“…Recently, the Hao, Zheng, Guo and Xiao group reported an iridium-catalyzed system for the trifluoromethylation of heteroarenes with TFSP as trifluoromethylating agent. [185] Finally, it ought to be mentioned that the Khusnutdinova group reported the use of nickel(III) complexes as photoactivatable reagents for the trifluoromethylation of (hetero)arenes. [215] These complexes not only enable direct stoichiometric trifluoromethylations but were also shown to enable catalytic trifluoromethylations with the Langlois' reagent in the presence of oxidants.…”

“…Recently, the Hao, Zheng, Guo and Xiao group reported an iridium‐catalyzed system for the trifluoromethylation of heteroarenes with TFSP as trifluoromethylating agent [185] . Finally, it ought to be mentioned that the Khusnutdinova group reported the use of nickel(III) complexes as photoactivatable reagents for the trifluoromethylation of (hetero)arenes [215] .…”

“…Similar to the Langlois' reagent, trifluoromethylsulfonyl-pyridinium salts can be synthesized from trifluoromethanesulfonic anhydride and also be used as a trifluoromethyl source. [185] These reagents are by far the most popular trifluoromethylating reagent and many systems have thus been described for direct trifluoromethylations of (hetero)arenes exploiting the inherent ability of such reagents to generate a trifluoromethyl radical species under oxidative/reducing conditions, with or without transition metals. These reactions will be presented in the next subsection, starting with metal-free oxidative systems.…”

“…Similar to the other zinc sulfinates, this reagent, which is commercially available but rather expensive, can be easily synthesized starting from the corresponding commercially available trifluoromethylsulfonyl chloride, upon reaction with zinc (Scheme 47, Equation (4)). Similar to the Langlois’ reagent, trifluoromethylsulfonyl‐pyridinium salts can be synthesized from trifluoromethanesulfonic anhydride and also be used as a trifluoromethyl source [185] …”