Visible-Light-Induced, Copper-Catalyzed Three-Component Coupling of Alkyl Halides, Olefins, and Trifluoromethylthiolate to Generate Trifluoromethyl Thioethers

Abstract

Photoinduced, copper-catalyzed coupling reactions are emerging as a powerful method for generating Csp^3–Y (Y = C or heteroatom) bonds from alkyl electrophiles and nucleophiles. Corresponding three-component couplings of alkyl electrophiles, olefins, and nucleophiles have the potential to generate an additional Csp3–Y bond and to efficiently add functional groups to both carbons of an olefin, which serves as a readily available linchpin. In this report, we establish that a variety of electrophiles and a trifluoromethylthiolate nucleophile can add across an array of olefins (including styrenes and electron-poor olefins) in the presence of CuI/binap and blue-LED irradiation, thereby generating trifluoromethyl thioethers in good yield. The process tolerates a wide range of functional groups, and an initial survey of other nucleophiles (i.e., bromide, cyanide, and azide) suggests that this three-component coupling strategy is versatile. Mechanistic studies are consistent with a photoexcited Cu(I)/binap/SCF_3 complex serving as a reductant to generate an alkyl radical from the electrophile, which likely reacts in turn with the olefin and a Cu(II)/SCF_3 complex to afford the coupling product.