Geometrically Selective Denitrative Trifluoromethylthiolation of β-Nitrostyrenes with AgSCF₃ for (E)-Vinyl Trifluoromethyl Thioethers

Abstract

An efficient copper­(II)-promoted denitrative trifluoromethylthiolation under mild reaction conditions has been developed for vinyl trifluoromethyl thioethers to construct Cvinyl–SCF3 bonds with stable AgSCF3 as a source of the trifluoromethylthio. This reaction system tolerates a broad range of functional groups to commendably achieve a high product yield and excellent stereoselectivity of E/Z.

Denitrative Cross-Couplings of Nitrostyrenes

“…Employment of state-of-the-art photochemical catalytic processes and electrochemical generation of radical species hold promises to solve this and other existing drawbacks. Without a doubt, many more efficient and unprecedented discoveries are ahead of us, as several relevant articles were published already during the preparation of this manuscript [ 65 , 66 ].…”

A regioselective synthesis of 3,4-diaryl-1H-pyrazoles through a 1,3-dipolar cycloaddition of tosylhydrazones and nitroalkenes

“…In a first effort, we used the reaction conditions previously reported 22 (Table 1, entry 1), and the nitroalkene (6a) was obtained in a low yield (14%). Other studies suggested carrying out the reaction at 0 °C; 23,24 however, the attempt was unsuccessful (Table 1, entries 2 and 3). Due to the negative results, we replaced sodium hydroxide with ammonium acetate in glacial acetic acid; 25 unfortunately, the yield did not improve (entry 4, 15%).…”

Direct Synthesis of Disubstituted Trifluoromethylthiolated Alkenes

“…The group of Hong reported in 2020 the efficient preparation of several SCF 3 -containing difunctionalized alkenes (Scheme 11). 31 The copper-promoted denitrative trifluoromethylthiolation of monosubstituted -nitrostyrenes 23a-g was achieved in good yields (up to 87% yield) by using reagent VII as the SCF 3 source. The approach turned out to be functional-group tolerant (e.g., CN, CO 2 Me, halogens).…”

“…Copper-catalyzed denitrative trifluoromethylthiolation of nitroalkenes. 31 E/Z ratios are given in parentheses and were determined by 19 F NMR analysis. Only the major isomer is depicted.…”