A Novel Nickel-Catalyzed Domino Method for the Direct Synthesis of Symmetrical Disulfides Using Potassium 5-Methyl-1,3,4-oxadiazole-2-thiolate as a Sulfurating Reagent

Abstract

A simple, one pot, efficient, and novel protocol has been developed for the direct synthesis of symmetrical organic disulfides using a domino reaction between an aryl/alkyl halide and potassium 5-methyl-1,3,4-oxadiazole-2-thiolate in the presence of NiCl₂ as catalyst. A variety of symmetrical aryl/alkyl disulfides can be obtained in moderate to excellent yields (up to 95%).

Key words

nickel-catalyzed - disulfides - cross-coupling - 1,3,4-oxadiazole - sulfur-transfer reagents

• References and Notes

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• 19 Symmetrical Organic Disulfide Synthesis; Typical Experimental Procedure A mixture of iodobenzene (2.0 mmol), potassium 5-methyl-1,3,4-oxadiazole-2-thiolate (1, 0.462 g, 3.0 mmol), NiCl₂·6H₂O (10 mol%) and KOH (1.0 g, 18 mmol) were added to a flask containing DMF–H₂O (2 mL, 20:1) and EG (0.11 mL, 2 mmol). The reaction mixture was heated at 130 °C under atmospheric conditions until completion, monitored by TLC. The reaction mixture was then filtered, the filtrate was evaporated under reduced pressure, CH₂Cl₂ (20 mL) was added, and the mixture was washed with H₂O (2 × 15 mL). The organic layer was dried over anhydrous Na₂SO₄, filtered, and the solvent was evaporated to give the crude diaryl/alkyl disulfide, which was purified by preparative TLC (silica gel; n-hexane–EtOAc, 20:1). Compound 3d was obtained as a creamy yellow solid in 75% yield; mp 94–97 °C. ¹H NMR (400 MHz, CDCl₃): δ = 8.41–8.50 (m, 2 H), 7.82–7.95 (m, 4 H), 7.34–7.7 (m, 8 H). ¹³C NMR (100 MHz, CDCl₃): δ = 134.1, 132.6, 130.3, 129.9, 128.6, 128.0, 126.8, 126.6, 125.9, 125.1. MS (EI): m/z = 318 [M⁺]. Compound 3f was obtained (EtOAc–n-hexane, 1:10) as a light green solid in 89% yield; mp 54–55 °C. ¹H NMR (400 MHz, CDCl₃): δ = 7.36–7.38 (m, 2 H), 7.22–7.25 (m, 2 H), 6.97–7.00 (m, 2 H). ¹³C NMR (100 MHz, CDCl₃): δ = 155.4, 129.7, 120.7, 115.4. Compound 3j was obtained (EtOAc–n-hexane, 1:5) as a white solid in 55% yield; mp 41–43 °C. ¹H NMR (400 MHz, CDCl₃): δ = 7.32 (d, J = 8.8 Hz, 4 H), 6.87 (d, J = 8.8 Hz, 4 H), 3.82 (s, 6 H). ¹³C NMR (100 MHz, CDCl₃): δ = 159.0, 132.8, 127.4, 114.7, 55.4. Compound 3k was obtained (EtOAc–n-hexane, 1:20) as a white solid in 90% yield; mp 68–70 °C. ¹H NMR (400 MHz, CDCl₃): δ = 7.28–7.38 (m, 10 H), 3.63 (s, 4 H). ¹³C NMR (100 MHz, CDCl₃): δ = 137.4, 129.5, 128.5, 127.5, 43.3.