Facile and General Electrochemical Diselenylation of Terminal Alkynes

Abstract

Difunctionalization of terminal alkynes is a cuttingedge method for producing trisubstituted alkenes. The methods employed, however, rely heavily on the use of organometallic species with harsh conditions or transition metal-catalyzed multicomponent radical-mediated transformations. Herein, we report an electrochemical diselenylation of terminal alkynes to afford trisubstituted alkenes in an antiselective fashion with 100% atom economy. Moreover, this method uses simple graphite as electrodes and MeCN as a solvent and does not require high temperatures, which affords trisubstituted alkenes with high regioselectivity. The success of the gram-scale reaction, great tolerance to multiple functional groups, and the functionalization of complex compounds all established the value of this green technology.

Electrochemical Synthesis of α-Thiocyanated/Methoxylated Ketones Using Enol Acetates

“…. 22 This is a known compound, and the spectroscopic data are consistent with those previously reported. The crude residue was purified by flash column chromatography (SiO 2 ; 8:1 PE/EA), 31 mg, 70% yield, yellow solid, mp 94.0−96.6 °C; 1 H NMR (600 MHz, CDCl 3 ): δ 7.88 (d, J = 8.9 Hz, 2H), 6.95 (d, J = 8.9 Hz, 2H), 4.69 (s, 2H), 4.13−4.10 (m, 2H), 1.45 (t, J = 6.9 Hz, 3H).…”

Recent advances in the dichalcogenation reactions of unsaturated compounds via double functionalization

“…Very recently, Wang and coworkers developed an electrochemical protocol for the diselenylation of terminal alkynes 45a with diselenides 45b under metal- and catalyst-free conditions in an atom- and step-economical manner (Scheme 45). 64 The reactions were carried out in an undivided cell using simple graphite as electrodes and n Bu 4 NBF 4 as an electrolyte at room temperature. An ample range of (hetero)aryl terminal alkynes and even internal alkynes were competent substrates for this transformation.…”

Recent progress in the electrochemical selenofunctionalization of alkenes and alkynes

“…50 Recently, Wang et al reported an electrochemically driven diselenylation of terminal alkynes to prepare 1,2-bis-selenyl alkenes (Scheme 14). 51 This method exhibits high tolerance toward various functional groups and is suitable for the late-stage functionalization of alkyne-functionalized drugs. Based on radical trapping experiments and HRMS data analysis, a plausible mechanistic scenario was proposed.…”