Stereoselective Synthesis of (Z)-β-Chlorovinyl Sulfones by Addition of Sulfonyl Chlorides to Acetylenes

Abstract

The addition reaction of sulfonyl chlorides with acetyl­enes in the presence of a copper salt is described. The reaction proceeds in toluene in the presence of CuCl with Me₂S as the additive to afford only (Z)-β-chlorovinyl sulfones in moderate to excellent yields.

Key words

halovinyl sulfones - sulfonyl chlorides - acetylenes - CuCl/Me₂S

References

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9

General procedure: To a solution of alkyne (1.0 mmol) and sulfonyl chloride (1.5 mmol) in toluene (5 mL) was added CuCl (0.1 mmol) and Me₂S (1.0 mmol). The reaction mixture was heated under argon to 110 °C for the time indicated. The mixture was then quenched by the addition of H₂O and extracted with diethyl ether. The isolated organic phase was dried over Na₂SO₄, filtered, concentrated in vacuo, and purified by column chromatography on silica gel eluting with ethyl acetate-hexane. 3f: mp 138-140 °C; IR (film): 1577, 1314, 1146, 562 cm^-1; ¹H NMR (CDCl₃, 300 MHz): δ = 7.12 (s, 1 H), 7.45-7.48 (m, 2 H), 7.52-7.60 (m, 4 H), 7.64-7.69 (m, 1 H), 8.06 (d, 2 H); ¹³C NMR (CDCl₃, 75 MHz): δ = 145.0, 140.4, 133.8, 132.0 (2 C), 129.1 (2 C), 128.6 (2 C), 128.1 (2 C), 127.9 (2 C), 126.3; MS (EI): m/z 356 (M⁺, 12), 233 (9), 205 (6), 180 (17), 152 (100), 125 (33), 101 (27), 77 (55).