Synthesis of Vinyl Trifluoromethyl Thioethers via Copper-Mediated Trifluoromethylthiolation of Vinyl Bromides

Abstract

A copper-mediated trifluoromethylthiolation of vinyl bromides has been developed. This method provides ready access to vinyl trifluoromethyl thioethers in good to high yields from simple, inexpensive starting materials. A broad substrate scope is achieved, and the reaction is compatible with various functional groups, including cyano, nitro, trifluoromethyl, alkoxy, amino, halide, and heterocyclic groups.

Nickel-catalyzed trifluoromethylthiolation of Csp2–O bonds

“…23 However, the current methodological repertoire to access these compounds relies predominantly on indirect strategies 24 or requiring stoichiometric amounts of metal. 13b , 25 The direct construction of C vinyl –SCF 3 in a catalytic manner would be a highly attractive approach. It has been accomplished via the Cu-catalyzed trifluoromethylthiolation of vinyl boronic acids with electrophilic SCF 3 -sources.…”

Advances in trifluoromethylation or trifluoromethylthiolation with copper $$\hbox {CF}_{3}$$ CF 3 or $$\hbox {SCF}_{3}$$ SCF 3 complexes

“…34,35 Vinyl trifluoromethyl thioethers 40 can be obtained in 23-93% yields by the reactions of vinyl bromides 39 with (bpy)Cu(SCF 3 ) in the presence of diglyme as solvent. 36 A plausible mechanism for the trifluoromethylthiolation of β-bromo-α, β-unsaturated ketones was proposed by Weng and co-workers, 35 as shown in Scheme 14. First of all, the 1, 4-addition of (bpy) CuSCF 3 to β-bromoα, β-unsaturated ketones 37 generated the intermediates A or B.…”

“…In 2014 and 2015, Weng and co-workers developed an efficient and convenient trifluoromethylthiolation of α-bromo-α,β-unsaturated carbonyl compounds 35, βbromo-α,β-unsaturated ketones 37, and vinyl bromides 39 to give the corresponding trifluoromethylthiolated products 36, 38 and 40 in moderate to good yields with (bpy)CuSCF 3 as SCF 3 source (Scheme 13). [34][35][36] When MeCN and xylene were used as solvent, under the conditions of 140 • C, the substrates 35 and 37, whether they are α-bromo-α,β-unsaturated aldehydes, ketone, esters, or β-bromo-α,β-unsaturated ketones, were shown to be well tolerated, and afforded the desired products 36 and 38 in 53-69% and 44-87% yields, respectively. 34,35 Vinyl trifluoromethyl thioethers 40 can be obtained in 23-93% yields by the reactions of vinyl bromides 39 with (bpy)Cu(SCF 3 ) in the presence of diglyme as solvent.…”

Recent Advances of Direct Incorporation of Fluorine-Containing Groups and 18F-Labeling Methods

“…该络合物成功被用于芳香 (杂)环卤化物 [63] 、苄基溴 [64] 、卤代烷 [65] 的三氟甲硫基化 反应. 最近, 通过对前期工作 [30] 的进一步研究, 该课题 组 [66] 随后, α-三氟甲硫基-α,β-不饱和羰基化合物的合 成 [67] 、β-三氟甲硫基-α,β-不饱和羰基化合物的合成 [68] , 以 及 乙 烯 基 三 氟 甲 基 硫 酯 的 合 成 [69]…”