Synlett 2014; 25(16): 2345-2349
DOI: 10.1055/s-0034-1378546
letter
© Georg Thieme Verlag Stuttgart · New York

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

Ganesh M. Shelke
Department of Chemistry, Birla Institute of Technology and Science, Pilani 333031, Rajasthan, India   Fax: +91(1596)244183   Email: anilkumar@pilani.bits-pilani.ac.in
,
V. Kameswara Rao
Department of Chemistry, Birla Institute of Technology and Science, Pilani 333031, Rajasthan, India   Fax: +91(1596)244183   Email: anilkumar@pilani.bits-pilani.ac.in
,
Kasiviswanadharaju Pericherla
Department of Chemistry, Birla Institute of Technology and Science, Pilani 333031, Rajasthan, India   Fax: +91(1596)244183   Email: anilkumar@pilani.bits-pilani.ac.in
,
Anil Kumar*
Department of Chemistry, Birla Institute of Technology and Science, Pilani 333031, Rajasthan, India   Fax: +91(1596)244183   Email: anilkumar@pilani.bits-pilani.ac.in
› Author Affiliations
Further Information

Publication History

Received: 19 May 2014

Accepted after revision: 29 June 2014

Publication Date:
26 August 2014 (online)


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.

Supporting Information

 
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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.