PAPER
Anion-Functionalized Ionic Liquids in CuI-Catalyzed Cross-Coupling Reactions
2955
13C NMR (100 MHz, CDCl3): d = 44.8, 55.7, 114.5, 129.5, 133.5,
163.7.
13C NMR (100 MHz, CDCl3): d = 43.3, 116.4 (d, JC–F = 21.8 Hz),
125.8 (d, JC–F = 2.1 Hz), 128.4 (d, JC–F = 4.3 Hz), 130.61 (d, JC–F
9.5 Hz), 142.67, 163.48 (d, JC–F = 251.9 Hz).
=
1-Methanesulfonyl-4-nitrobenzene (2d)
Yellow solid; mp 125–126 °C (Lit.7b 125 °C).
Phenyl (E)-2-Phenylethenyl Sulfone (3d)
Yellow solid; mp 72–73 °C (Lit.18 74.5–75.5 °C).
1H NMR (400 MHz, CDCl3): d = 3.14 (s, 3 H), 8.16 (d, J = 8.7 Hz,
2 H), 8.43 (d, J = 8.7 Hz, 2 H).
IR (KBr): 3056, 1613, 1448, 1302, 1146, 1086, 972 cm–1.
1H NMR (400 MHz, CDCl3): d = 6.86 (d, J = 15.2 Hz, 1 H), 7.39
(m, 3 H), 7.48 (m, 2 H), 7.55 (m, 2 H), 7.61 (m, 1 H), 7.69 (d,
J = 15.2 Hz, 1 H), 7.95 (m, 2 H).
13C NMR (100 MHz, CDCl3): d = 127.6, 127.3, 127.6, 128.6, 129.1,
129.3, 131.2, 132.3, 133.4, 140.7, 142.5, 142.5.
1-Methanesulfonyl-2-nitrobenzene (2e)
Yellow solid; mp 135–136 °C.
1H NMR (400 MHz, CDCl3): d = 3.16 (s, 3 H), 7.85 (t, J = 8.0 Hz,
1 H), 8.32 (d, J = 7.8 Hz, 1 H), 8.53 (m, 1 H), 8.82 (t, J = 2.0 Hz,
1 H).
13C NMR (100 MHz, CDCl3): d = 44.4, 122.9, 128.3, 130.9, 133.0,
142.6, 149.4.
(E)-2-(4-Methylphenyl)ethenyl Phenyl Sulfone (3e)
Colorless solid; mp 132–134 °C (Lit.19 135.5–136.5 °C).
1H NMR (400 MHz, CDCl3): d = 2.34 (s, 3 H), 6.78 (d, J = 15.2 Hz,
1 H), 7.16 (d, J = 7.2 Hz, 2 H), 7.35 (d, J = 8.0 Hz, 2 H), 7.49–7.58
(m, 3 H), 7.63 (d, J = 15.6 Hz, 1 H), 7.92 (d, J = 8.0 Hz, 2 H).
13C NMR (100 MHz, CDCl3): d = 21.5, 126.1, 127.6, 128.6, 129.3,
129.6, 129.8, 133.2, 140.9, 141.8, 142.5.
2-Methanesulfonylthiophene (2f)
Colorless solid; mp 46–47 °C (Lit.7b 47 °C).
1H NMR (400 MHz, CDCl3): d = 3.19 (s, 3 H), 7.15 (m, 1 H), 7.70
(m, 2 H).
IR (KBr): 3054, 2920, 1605, 1308, 1447, 1177, 1084, 974 cm–1.
HRMS (ESI): m/z [M + Na]+ calcd for C15H14O2SNa: 281.0607;
Coupling Reaction of Sulfinic Salts and Vinyl Bromides; Gen-
eral Procedure
A mixture of sulfinic salt (1.2 mmol), vinyl bromide (1 mmol), CuI
(0.1 mmol), [emim][Val] (0.2 mmol) and DMSO (2 mL) was heated
at 100 °C for 48 h in air. After cooling, the mixture was partitioned
between Et2O (10 mL) and H2O (10 mL) and the organic layer was
separated. The aqueous layer was extracted with Et2O (2 × 5 mL)
and the combined organic layers were washed with brine (2 × 10
mL), dried over Na2SO4, and concentrated in vacuo. The residual oil
was purified by column chromatography (n-hexane–EtOAc) to af-
ford vinyl sulfones 3.
found: 281.0605.
(E)-2-(4-Fluorophenyl)ethenyl Phenyl Sulfone (3f)
Yellow solid; mp 108–110 °C.
IR (KBr): 3426, 3049, 3071, 1660, 1614, 1600, 1511, 1231, 1146,
1085, 993, 777 cm–1.
1H NMR (400 MHz, CDCl3): d = 6.78(d, J = 15.6 Hz, 1 H), 7.07 (t,
J = 8.6 Hz, 2 H), 7.47 (m, 2 H), 7.54 (t, J = 7.4 Hz, 2 H), 7.62 (t,
J = 2.4 Hz, 1 H), 7.64 (d, J = 15.2 Hz, 1 H), 7.93 (d, J = 8.0 Hz,
1 H), 7.95 (s, 1 H).
Methyl (E)-2-Phenylethenyl Sulfone (3a)
Colorless solid; mp 78–79 °C (Lit.16 79–80 °C).
13C NMR (100 MHz, CDCl3): d = 116.3 (d, JC–F = 21.9 Hz), 127.0
1
2
(t, JC–F = 2.4 Hz, JC–F = 3.8 Hz), 127.6, 128.6 (d, JC–F = 3.3 Hz),
IR (KBr): 3048, 3026, 2927, 1625, 1452, 1279, 1135, 1116, 996,
972 cm–1.
129.3, 130.6 (d, JC–F = 8.8 Hz), 133.4, 140.6, 141.1, 164.3 (d, JC–F
=
250.7 Hz).
1H NMR (400 MHz, CDCl3): d = 3.04 (s, 3 H), 6.96 (d, J = 14.8 Hz,
1 H), 7.40 (m, 3 H), 7.52 (m, 2 H), 7.62 (d, J = 15.6 Hz, 1 H).
13C NMR (100 MHz, CDCl3): d = 43.2, 126.2, 126.2, 128.6, 129.1, Acknowledgment
131.4, 132.1, 143.9.
We are grateful to the Science and Technology Commission of Zhe-
jiang Province (Grant Nos. 2007C21G2010067), and National Na-
tural Science Foundation of China (Grant Nos. 20672096) for their
financial support.
Methyl (E)-2-(4-Methylphenyl)ethenyl Sulfone (3b)
Colorless solid; mp 107–109 °C (Lit.17 109–110 °C).
IR (KBr): 3042, 3007, 2926, 1607, 1298, 1181, 1132, 973 cm–1.
1H NMR (400 MHz, CDCl3): d = 2.39 (s, 3 H), 3.03 (s, 3 H), 6.87
(d, J = 15.2 Hz, 1 H), 7.23 (d, J = 7.6 Hz, 2 H), 7.41 (d, J = 8.0 Hz,
2 H), 7.59 (d, J = 15.2 Hz, 1 H).
13C NMR (100 MHz, CDCl3): d = 21.5, 43.3, 125.0, 128.6, 129.3,
129.9, 142.0, 143.9.
HRMS (ESI): m/z [M + Na]+ calcd for C10H12O2SNa: 219.0450;
found: 219.0458.
References
(1) For some recent references, see: (a) Otzen, T.; Wempe, E.
G.; Kunz, B.; Bartels, R.; Lehwark-Yvetot, G.; Hänsel, W.;
Schaper, K.-J.; Seydel, J. K. J. Med. Chem. 2004, 47, 240.
(b) Sun, Z. Y.; Botros, E.; Su, A. D.; Kim, Y.; Wang, E.;
Baturay, N. Z.; Kwon, C. H. J. Med. Chem. 2000, 43, 4160.
(c) Hu, W.; Guo, Z.; Chu, F.; Bai, A.; Yi, X.; Cheng, G.; Li,
J. Bioorg. Med. Chem. Lett. 2003, 13, 1153. (d) Artico, M.;
Silvestri, R.; Pagnozzi, E.; Bruno, B.; Novellino, E.; Greco,
G.; Massa, S.; Ettorre, A.; Loi, A. G.; Scintu, F.; La Colla, P.
J. Med. Chem. 2000, 43, 1886. (e) Faucher, A.-M.; White,
P. W.; Brochu, C.; Grand-Maitre, C.; Rancourt, J.; Fazal, G.
J. Med. Chem. 2004, 47, 18.
(E)-2-(4-Fluorophenyl)ethenyl Methyl Sulfone (3c)
Pale-yellow solid; mp 124–126 °C (Lit.17 128–129 °C).
IR (KBr): 3054, 3017, 3068, 2932, 1621, 1599, 1509, 1300, 1162,
977 cm–1.
1H NMR (400 MHz, CDCl3): d = 3.04 (s, 3 H), 6.86 (d, J = 15.6 Hz,
1 H), 7.12 (m, 2 H), 7.52 (m, 2 H), 7.59 (d, J = 15.6 Hz, 1 H).
(2) Simpkins, N. S. Sulfones in Organic Synthesis; Pergamon
Press: Oxford, 1993.
Synthesis 2007, No. 19, 2951–2956 © Thieme Stuttgart · New York