An easily available, air/moisture insensitive and broadly applicable electrophilic reagent trifluoromethyl-substituted selenium ylide 1a and its reactions with a variety of nucleophiles including β-ketoesters and silyl enol ethers, aryl/heteroaryl boronic acids, electron-rich heteroarenes and sulfinates were described.
Trifluoromethylative
difunctionalization of alkenes with a variety
of nucleophiles including amine, azide, alcohol, water, and electron-rich
arenes using reagent 1 as trifluoromethyl radical source
in the presence of a synergistic catalyst including a Lewis acid scandium(III)
trifluoromethanesulfonate (Sc(OTf)3) and a photoredox catalyst
[fac-Ir(ppy)3] was described. Mechanistic
studies showed that the role of Sc(OTf)3 in the reaction
is to activate reagent 1 via Lewis acid–Lewis
base interaction to form complex [Sc(OTf)3•3(1)], which was fully characterized by nuclear magnetic resonance
(NMR) spectroscopy, mass spectrometry, and elemental analysis. Cyclic
voltammetry (CV) experiments and density functional theory (DFT) calculation
showed that the reduction potential of complex [Sc(OTf)3•3(1)] is much higher than that of reagent 1, thus suggesting complex [Sc(OTf)3•3(1)] is much easier to accept electron through single-electron-transfer
(SET) process, and consequently, much easier to generate trifluoromethyl
radical.
scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.