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 Me2 S as the additive to afford only (Z )-β-chlorovinyl sulfones in moderate to excellent yields.
Key words
halovinyl sulfones - sulfonyl chlorides - acetylenes - CuCl/Me2 S
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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 Me2 S (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 H2 O and extracted with diethyl ether. The isolated organic phase was dried over Na2 SO4 , 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 ; 1 H 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); 13 C 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).
CuX·Me2 S (X = I, Br) complex is an excellent catalyst for some conjugate addition reactions,
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