Direct C–H trifluoromethylation of di- and trisubstituted alkenes by photoredox catalysis

Background: Trifluoromethylated alkene scaffolds are known as useful structural motifs in pharmaceuticals and agrochemicals as well as functional organic materials. But reported synthetic methods usually require multiple synthetic steps and/or exhibit limitation with respect to access to tri- and tetrasubstituted CF(3)-alkenes. Thus development of new methodologies for facile construction of C(alkenyl)–CF(3) bonds is highly demanded. Results: The photoredox reaction of alkenes with 5-(trifluoromethyl)dibenzo[b,d]thiophenium tetrafluoroborate, Umemoto’s reagent, as a CF(3) source in the presence of [Ru(bpy)(3)](2+) catalyst (bpy = 2,2’-bipyridine) under visible light irradiation without any additive afforded CF(3)-substituted alkenes via direct C(alkenyl)–H trifluoromethylation. 1,1-Di- and trisubstituted alkenes were applicable to this photocatalytic system, providing the corresponding multisubstituted CF(3)-alkenes. In addition, use of an excess amount of the CF(3) source induced double C–H trifluoromethylation to afford geminal bis(trifluoromethyl)alkenes. Conclusion: A range of multisubstituted CF(3)-alkenes are easily accessible by photoredox-catalyzed direct C–H trifluoromethylation of alkenes under mild reaction conditions. In particular, trifluoromethylation of triphenylethene derivatives, from which synthetically valuable tetrasubstituted CF(3)-alkenes are obtained, have never been reported so far. Remarkably, the present facile and straightforward protocol is extended to double trifluoromethylation of alkenes.