Nickel-Catalyzed Decarbonylative Thioetherification of Carboxylic Acids with Thiols

Abstract

A nickel-catalyzed decarbonylative thioetherification of carboxylic acids with thiols was developed. Under the reaction conditions, benzoic acids, cinnamic acids, and benzyl carboxylic acids coupled with various thiols including both aromatic and aliphatic ones produce the corresponding thioethers in up to 99% yields. Moreover, this reaction was applicable to the modification of bioactive molecules such as 3-methylflavone-8-carboxylic acid, probenecid, and flufenamic acid, and the synthesis of acaricide chlorbenside. These results well demonstrated the potential synthetic value of this new reaction in organic synthesis.

Nonbasic Synthesis of Thioethers via Nickel-Catalyzed Reductive Thiolation Utilizing NBS-Like N-Thioimides as Electrophilic Sulfur Donors

“…1 H NMR (400 MHz, CDCl 3 ) δ 7.29 (2H, d, J = 8.1 Hz), 7.22 (2H, d, J = 8.6 Hz), 7.14–7.18 (4H, m), 2.35 (3H, s); 13 C NMR (101 MHz, CDCl 3 ) δ 138.2, 136.1, 132.6, 132.4, 130.9, 130.8, 130.3,129.3, 21.3. Spectra were consistent with literature data …”

“…1 H NMR (400 MHz, CDCl 3 ) δ 7.46 (2H, d, J = 8.3 Hz), 7.41 (2H, d, J = 8.2 Hz), 7.20–7.24 (4H, m), 2.40 (3H, s); 13 C­{ 1 H} NMR (101 MHz, CDCl 3 ) δ 160.8, 145.0, 136.9, 127.2 (q, J C–F = 33.0 Hz), 126.5, 125.7 (q, J C–F = 3.8 Hz), 124.3 (q, J C–F = 273.0 Hz), 121.7, 115.5, 55.5. Spectra were consistent with literature data …”

“…Spectra were consistent with literature data. 24 4,4,5,5-Tetramethyl-2-(4-(p-tolylthio)phenyl)-1,3,2-dioxaborolane Eluent: 250:1−100:1 petroleum ether/ethyl acetate, and the title compound was isolated as a white solid (147 mg, 0.451 mmol, 90.2% yield). R f = 0.8 (petroleum ether/ethyl acetate = 50:1).…”

“…R f = 0.7 (petroleum ether/ethyl acetate = 50:1). 1 24 p-Tolyl(4-(trifluoromethyl)phenyl)sulfane 3. Eluent: 250:1−100:1 petroleum ether/ethyl acetate, and the title compound was isolated as a white solid (111 mg, 0.415 mmol, 83.1% yield).…”

“…Spectra were consistent with literature data. 24 lane 3d. Eluent: 250:1−100:1 ether/ethyl acetate, and the title compound was isolated as a white solid (147 mg, 0.451 mmol, 90.2% yield).…”