An Efficient and Facile Synthesis of Vinyl Sulfones via Microwave-Assisted Copper Triflate Catalyzed Hydrosulfonylation of Alkynes

Abstract

An efficient method has been described for the synthesis of vinyl sulfones via hydrosulfonylation of alkynes using sodium arene sulfinates catalyzed by Cu(OTf)₂ under microwave irradiation. A variety of vinyl sulfones was obtained in good to excellent (71–89%) yields and with high regio- and stereoselectivity. Shortened reaction times, simple reaction conditions and low catalyst loading are the salient features of this protocol.

Key words

microwave - vinyl sulfones - copper triflate - alkynes - sodium arene sulfinates

• References and Notes

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• 22 Representative Procedure: Phenylacetylene (102 mg, 1 mmol), sodium benzene sulfinate (164 mg, 1 mmol), and Cu(OTf)₂ (16 mg, 2.5 mol%) were added to a 10-mL microwave tube containing AcOH (2 mL) and a magnetic stirrer bar. The reaction mixture was placed in a CEM Discover BenchMate. The reaction parameters were set to 200 W, 250 psi, 110 °C for 5 min with stirring. After completion of the reaction, the reaction mixture was diluted with H₂O (10 mL) and extracted with EtOAc (2 × 10 mL). The organic layer was dried with anhyd Na₂SO₄, filtered and the solvent evaporated on a rotary evaporator to give the crude product which was purified by passing through a silica column to give pure 3a (200 mg, 82%) as a white solid. Selected Spectroscopic Data: (E)-1-Methyl-3-[2-(phenylsulfonyl)vinyl]benzene (3c): yellow solid; mp 74–76 °C. ¹H NMR (400 MHz, CDCl₃): δ = 7.95–7.99 (m, 2 H), 7.68 (d, J = 15.4 Hz, 1 H), 7.61–7.65 (m, 1 H), 7.54–7.60 (m, 2 H), 7.29–7.33 (m, 3 H), 7.23–7.26 (m, 1 H), 6.87 (d, J = 15.4 Hz, 1 H), 2.37 (s, 3 H). ¹³C NMR (101 MHz, CDCl₃): δ = 142.71, 140.81, 138.87, 133.35, 132.31, 132.08, 129.34, 129.16, 128.99, 127.65, 127.00, 125.85, 21.28. IR (KBr): 3047, 2916, 1612, 1443, 1296, 1142 cm^–1. HRMS: m/z [M + H]⁺ calcd for C₁₅H₁₅O₂S: 259.0787; found: 259.0765. (E)-1-Ethyl-4-[2-(phenylsulfonyl)vinyl]benzene (3d): yellow solid; mp 95–96 °C. ¹H NMR (400 MHz, CDCl₃): δ = 7.95–7.99 (m, 2 H), 7.69 (d, J = 15.4 Hz, 1 H), 7.61–7.66 (m, 1 H), 7.54–7.59 (m, 2 H), 7.43 (d, J = 8.2 Hz, 2 H), 7.24 (d, J = 8.1 Hz, 2 H), 6.84 (d, J = 15.4 Hz, 1 H), 2.68 (q, J = 7.6 Hz, 2 H), 1.25 (t, J = 7.6 Hz, 3 H). ¹³C NMR (101 MHz, CDCl₃): δ = 148.19, 142.63, 140.94, 133.31, 129.85, 129.33, 128.74, 128.67, 127.61, 126.10, 28.86, 15.31. IR (KBr): 3055, 2962, 1612, 1512, 1450, 1311, 1149 cm^–1. HRMS: m/z [M + H]⁺ calcd for C₁₆H₁₇O₂S: 273.0944; found: 273.0958. (E)-1-Fluoro-4-(2-tosylvinyl)benzene (3l): white solid; mp 95–96 °C. ¹H NMR (400 MHz, CDCl₃): δ = 7.84 (d, J = 8.3 Hz, 2 H), 7.64 (d, J = 15.4 Hz, 1 H), 7.46–7.52 (m, 2 H), 7.36 (d, J = 8.0 Hz, 2 H), 7.09 (t, J = 8.6 Hz, 2 H), 6.81 (d, J = 15.4 Hz, 1 H), 2.45 (s, 3 H). ¹³C NMR (101 MHz, CDCl₃): δ = 164.30 (d, J _C–F = 252.8 Hz), 144.49, 140.61, 137.65, 130.56 (d, J _C–F = 8.7 Hz), 130.02, 128.72 (d, J _C–F = 3.4 Hz), 127.72, 127.41 (d, J _C–F = 2.4 Hz), 116.31 (d, J _C–F = 22.1 Hz), 21.64. IR (KBr): 3055, 1597, 1504, 1450, 1304, 1234, 1142 cm^–1 _. HRMS: m/z [M + H]⁺ calcd for C₁₅H₁₄FO₂S: 277.0693; found: 277.0685. (E)-2-(2-Tosylvinyl)pyridine (3o): yellow solid; mp 98–99 °C. ¹H NMR (400 MHz, CDCl₃): δ = 8.62 (d, J = 3.9 Hz, 1 H), 7.85 (d, J = 8.3 Hz, 2 H), 7.74 (td, J = 7.7, 1.8 Hz, 1 H), 7.64 (d, J = 14.9 Hz, 1 H), 7.43 (dd, J = 13.5, 11.4 Hz, 2 H), 7.35 (d, J = 8.0 Hz, 2 H), 7.28–7.32 (m, 1 H), 2.44 (s, 3 H). ¹³C NMR (101 MHz, CDCl₃): δ = 151.11, 150.29, 144.61, 140.03, 137.25, 137.04, 132.15, 130.00, 127.94, 125.39, 124.94, 21.65. IR (KBr): 3040, 1620, 1589, 1435, 1311, 1142 cm^–1 _. HRMS: m/z [M + H]⁺ calcd for C₁₄H₁₄NO₂S: 260.0740; found: 260.0725.