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Synlett 2012; 23(8): 1245-1249
DOI: 10.1055/s-0031-1290934
letter
© Georg Thieme Verlag Stuttgart · New York

Copper-Catalyzed Oxidative Hydrosulfonylation of Alkynes Using Sodium Sulfinates in Air

Nobukazu Taniguchi*
Department of Chemistry, Fukushima Medical University, Fukushima 960-1295, Japan, Fax: +81(24)5471369   Email: taniguti@fmu.ac.jp
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Further Information

Publication History

Received: 19 January 2012

Accepted after revision: 09 March 2012

Publication Date:
26 April 2012 (online)

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Abstract

Copper-catalyzed hydrosulfonylations of alkynes can be carried out using sodium sulfinates in air. The procedure affords syn-selectively (E)-alkenyl sulfones in good yields. Then, both terminal and internal alkynes are available.

Key words

(E)-alkenyl sulfone - hydrosulfonylation - copper catalyst - alkyne - sodium sulfinate

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    for this article is available online at http://www.thieme-connect.com/ejournals/toc/synlett.
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  • 8 Typical Procedure for Hydrosulfonylation of Alkynes: To a mixture of CuCl (1.5 mg, 0.015 mmol), 2,2′-bis(2-oxazoline) (2.1 mg, 0.015 mmol), and PhSO2Na (2a; 54.2 mg, 0.33 mmol), in DMSO (0.1 mL), H2O (0.1 mL) and AcOH (0.1 mL) was added phenylacetylene (1a; 30.6 mg, 0.3 mmol), and the mixture was stirred at 60 ° C for 18 h in air. After the residue was dissolved in Et2O, the solution was washed with H2O and sat. NaCl and dried over anhyd MgSO4. Chromatography on silica gel (40% Et2O–hexane) gave phenyl (E)-2-phenylethenyl sulfone (3aa; 61.8 mg, 85%). 1H NMR (270 MHz, CDCl3): δ = 7.96 (d, J = 8.2 Hz, 2 H), 7.68 (d, J = 15.5 Hz, 1 H), 7.30–7.58 (m, 8 H), 6.87 (d, J = 15.5 Hz, 1 H). 13C NMR (67.5 MHz, CDCl3): δ = 142.4, 140.6, 133.3, 132.2, 131.1, 129.3, 128.9, 128.5, 127.6, 127.2. IR (CHCl3): 1613, 1447, 1306, 1146 cm–1. Anal. Calcd for C14H12O2S: C, 68.83; H, 4.95. Found: C, 68.56; H, 5.02

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  • 10 Typical Procedure for Gram-Scale Hydrosulfonylation of Alkynes: To a mixture of CuCl (49.5 mg, 0.5 mmol), 2,2′-bis(2-oxazoline) (70.1 mg, 0.5 mmol), and 4-MeC6H4SO2Na (2b; 1.9 g, 11 mmol), in DMSO (3 mL), H2O (3 mL) and AcOH (3 mL) was added phenylacetylene (1a; 10.0 g, 10.0 mmol), and the mixture was stirred at 60 °C for 18 h in air. After the residue was dissolved in Et2O, the solution was washed with H2O and sat. NaCl and dried over anhyd MgSO4. Chromatography on silica gel (40% Et2O–hexane) gave 4-tolyl (E)-2-phenylethenyl sulfone (3ab; 1.78 g, 78%). 1H NMR (270 MHz, CDCl3): δ = 7.83 (d, J = 8.2 Hz, 2 H), 7.65 (d, J = 15.5 Hz, 1 H), 7.45–7.49 (m, 2 H), 7.32–7.40 (m, 5 H), 6.85 (d, J = 15.5 Hz, 1 H), 2.43 (s, 3 H). 13C NMR (67.5 MHz, CDCl3): δ = 144.3, 141.9, 137.8, 132.4, 131.1, 129.9, 129.0, 128.5, 127.7, 127.6, 21.5. IR (CHCl3): 1614, 1449, 1302, 1145 cm–1. Anal. Calcd for C15H14O2S: C, 69.74; H, 5.46. Found: C, 69.38; H, 5.46