Electrochemical Synthesis of Vinyl Sulfones by Sulfonylation of Styrenes with a Catalytic Amount of Potassium Iodide

Abstract

An electrochemical sulfonylation reaction of styrenes was developed in which sodium arylsulfinates were used as sulfonylating reagents, a catalytic amount of KI was used as a redox mediator, and Bu₄NBF₄ was used as the electrolyte. In addition to various styrenes, sodium arylsulfinates with either electron-donating or electron-withdrawing groups were tolerated.

Key words

electrochemical synthesis - vinyl sulfones - sulfonylation - styrenes - sodium sulfinates

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• 13 Electrochemical Sulfonylation of Styrenes 3a–w; General Procedure An undivided cell equipped with a Pt anode (1.0 × 1.0 × 0.02 cm) and a graphite rod cathode was charged with the appropriate sodium arylsulfinate (2 mmol), KI (0.5 mmol), and Bu₄NBF₄ (1 mmol). The vessel was evacuated and backfilled with N₂ (×3). The appropriate styrene (1 mmol), DMSO (3 mL), and AcOH (3 mL) were added sequentially from a syringe. Electrolysis was carried out at a constant current of 12 mA at 50 °C for 10 h. The mixture was then cooled to rt and filtered through a plug of silica, eluting with EtOAc. The filtrate was washed with H₂O (×3) and extracted with EtOAc. The organic layer was washed with brine, dried (Na₂SO₄), and evaporated to dryness under reduced pressure. The residue was purified by column chromatography [silica gel, PE–EtOAc (5:1)].
• 14 (E)-2-Phenylvinyl 4-Tolyl Sulfone (3a) White solid; yield: 209.4 mg (81%); mp 119–120 °C. ¹H NMR (600 MHz, CDCl₃): δ = 7.83 (d, J = 8.3 Hz, 2 H), 7.66 (d, J = 15.4 Hz, 1 H), 7.48–7.47 (m, 2 H), 7.42–7.34 (m, 5 H), 6.85 (d, J = 15.4 Hz, 1 H), 2.43 (s, 3 H). ¹³C NMR (151 MHz, CDCl₃): δ = 144.5, 142.1, 137.8, 132.6, 131.2, 130.1, 129.2, 128.7, 127.8, 127.7, 21.8. HRMS (ESI): m/z [M + H]⁺ calcd for C₁₅H₁₅O₂S: 259.0787; found: 259.0789. (E)-4-(2-Tosylvinyl)benzonitrile (3h) White solid; yield: 234.6 mg (83%); mp 125–127 °C. ¹H NMR (600 MHz, CDCl₃): δ = 7.83 (d, J = 8.3 Hz, 2 H), 7.69 (d, J = 8.3 Hz, 2 H), 7.65 (d, J = 15.5 Hz, 1 H), 7.58 (d, J = 8.3 Hz, 2 H), 7.37 (d, J = 8.0 Hz, 2 H), 6.96 (dd, J = 15.4, 0.8 Hz, 1 H), 2.45 (s, 3 H). ¹³C NMR (151 MHz, CDCl₃): δ = 145.1, 139.4, 136.9, 136.8, 132.9, 131.4, 130.3, 129.0, 128.1, 118.2, 114.3, 21.8. HRMS (ESI): m/z [M + H]⁺ calcd for C₁₆H₁₄NO₂S: 284.0740; found: 284.0738. (E)-2-(2-Naphthyl)vinyl 4-Tolyl Sulfone (3k) Yellow solid; yield: 246.9 mg (80%); mp 160–162 °C. ¹H NMR (400 MHz, CDCl₃): δ = 7.91–7.79 (m, 7 H), 7.54–7.49 (m, 3 H), 7.34 (d, J = 7.9 Hz, 2 H), 6.96 (d, J = 15.4 Hz, 1 H), 2.42 (s, 3 H). ¹³C NMR (101 MHz, CDCl₃): δ = 144.5, 142.1, 137.9, 134.5, 133.2, 131.0, 130.1, 130.0, 129.0, 128.8, 127.9, 127.8, 127.7, 127.1, 123.5, 21.7. HRMS (ESI): m/z [M + H]⁺ calcd for C₁₉H₁₇O₂S: 309.0944; found: 309.0948. 2-Chlorophenyl (E)-2-Phenylvinyl Sulfone (3v) White solid; yield: 247.8 mg (89%); mp 93–94 °C. ¹H NMR (400 MHz, CDCl₃): δ = 8.22 (d, J = 7.7 Hz, 1 H), 7.77 (d, J = 15.4 Hz, 1 H), 7.57–7.39 (m, 8 H), 7.08 (d, J = 15.4 Hz, 1 H). ¹³C NMR (101 MHz, CDCl₃): δ = 145.4, 138.2, 134.6, 132.9, 132.4, 132.0, 131.5, 130.8, 129.2, 128.8, 127.6, 125.3. HRMS (ESI): m/z [M + H]⁺ calcd for C₁₄H₁₅ClNO₂S: 296.0507; found: 296.0513 2-Phenylprop-2-en-1-yl 4-Tolyl Sulfone (3w) White solid; yield: 197.9 mg (73%); mp 97–98 °C. ¹H NMR (400 MHz, CDCl₃): δ = 7.67–7.64 (m, 2 H), 7.29–7.21 (m, 7 H), 5.59 (s, 1 H), 5.21 (s, 1 H), 4.25 (s, 2 H), 2.39 (s, 3 H). ¹³C NMR (151 MHz, CDCl₃): δ = 144.7, 139.0, 136.7, 135.5, 129.6, 128.8, 128.5, 128.0, 126.3, 121.9, 62.2, 21.7. HRMS (ESI): m/z [M + H]⁺ calcd for C₁₆H₁₆NaO₂S: 295.0763; found: 295.0765.