3060
S. H. Chanteau, J. M. Tour / Tetrahedron Letters 42 (2001) 3057–3060
5. (a) Ziessel, R.; Suffert, J.; Youinou, M.-T. J. Org. Chem.
325.0851, found: 325.0847. 4: IR (KBr) 3730.2, 3438.6,
1996, 61, 6535; (b) Champness, N. R.; Khlobystov, A.
N.; Majuga, A. G.; Schro¨der, M.; Zyk, N. V. Tetrahedron
Lett. 1999, 40, 5413; (c) Whiteford, J. A.; Lu, C. V.;
Stang, P. J. J. Am. Chem. Soc. 1997, 119, 2524; (d)
Ziessel, R.; Suffert, J. Tetrahedron Lett 1991, 32, 757.
6. Sonogashira, K.; Tohda, Y.; Hagihara, N. Tetrahedron
Lett. 1975, 50, 4467.
7. Coudret, C. Synth. Commun. 1996, 26 (19), 3543.
8. Typical procedure for the in-situ removal of the TMS
protecting group and the Sonogashira coupling: To a solu-
tion of the aryl bromide (1.0 mmol), K2CO3 (5.0 mmol),
bis(triphenylphosphine)palladium(II) dichloride (0.05
mmol), copper(I) iodide (0.05 mmol) and triphenylphos-
phine (0.20 mmol) in THF (2 mL) under nitrogen were
added via a cannula 1 (1.20 mmol) in THF (2 mL) and
MeOH (1 mL). The mixture was heated at 60°C for 12
h–2 days. The solvent was removed by rotary evapora-
tion and the brown residue was diluted with water and
extracted with Et2O. The combined organic layers were
dried over Na2SO4, filtered and the solvent evaporated in
vacuo. Purification by flash chromatography (silica gel)
afforded the title compound.
2204.8, 1592.4, 1541.1, 1409.8, 1308.5, 1249.9, 818.8
cm−1 1H NMR (400 MHz, CDCl3) l 8.67 (dd, J=4.4,
.
1.7 Hz, 2H), 8.65 (dd, J=4.5, 1.7 Hz, 2H), 8.34 (s, 1H),
7.44 (dd, J=4.5, 1.7 Hz, 2H), 7.40 (dd, J=4,4, 1.6 Hz,
2H), 6.99 (s, 1H), 5.03 (br s, 2H). 13C NMR (100 MHz,
CDCl3) l 151.26, 150.03, 149.90, 139.56, 130.71, 130.52,
130.00, 125.65, 125.33, 120.33, 118.52, 106.57, 94.67,
94.19, 89.55, 87.27. HRMS calcd for C20H12N4O2:
340.0960, found: 340.0958. 8: IR (KBr) 3438.2, 3195.9,
2922.4, 1695.4, 1627.7, 1596.5, 1545.1, 1514.8, 1477.2,
.
1402.8, 1316.4, 1249.9 cm−1 1H NMR (400 MHz,
DMSO-d) l 8.68 (br d, J=4.0 Hz, 2H), 8.23 (s, 1H), 7.79
(d, J=8.1 Hz, 2H), 7.54 (d, J=5.0 Hz, 2H), 7.49 (d,
J=8.0 Hz, 2H), 7.13 (br s, 2H), 7.06 (s, 1H), 2.46 (s, 3H).
13C NMR (100 MHz, DMSO-d) l 192.98, 153.79, 150.13,
136.28, 134.31, 132.32, 130.69, 129.67, 128.66, 125.34,
123.05, 118.70, 118.26, 105.43, 95.72, 92.51, 90.12, 85.54,
30.32. HRMS calcd for C23H15N3O3S: 413.0834, found:
413.0940. 10: IR (KBr) 3445.3, 3046.3, 2203.5, 1548.5,
1529.1, 1399.9, 1341.6 cm−1. 1H NMR (400 MHz, CDCl3)
l 8.67 (br d, J=4.9 Hz, 2H), 8.27 (d, J=1.5 Hz, 1H),
7.76 (1/2 ABqd, J=8.0, 1.6 Hz, 1H), 7.72 (1/2 ABqd,
J=8.0, 0.5 Hz, 1H), 7.56 (m, 2H), 7.45 (dd, J=5.9, 1.7
Hz, 2H), 7.40 (m, 3H). 13C NMR (100 MHz, CDCl3) l
149.58, 135.39, 134.65, 131.81, 129.34, 128.54, 127.67,
125.32, 121.85, 116.66, 95.30, 94.30, 88.52, 86.63. HRMS
calcd for C21H12N2O2: 324.0899, found: 324.0895. 12: IR
(KBr) 3442.3, 3053.0, 2209.4, 1631.3, 1584.8, 1524.7,
9. (a) Tour, J. M.; Lamba, J. J. S. J. Am. Chem. Soc. 1993,
115, 4935; (b) Lamba, J. J. S.; Tour, J. M. J. Am. Chem.
Soc. 1994, 116, 11723; (c) Moroni, M.; Le Moigne, J.;
Pham, T. A.; Bigot, J.-Y. Macromolecules 1997, 30, 1964.
10. Rosen, G. M.; Tsai, P.; Barth, E. D.; Dorey, G.; Casara,
P.; Spedding, M.; Halpern, H. J. J. Org. Chem. 2000, 65,
4460.
1404.3, 1344.7, 1269.0, 826.4, 755.2, 686.6 cm−1 1H
.
11. Pearson, D. L.; Tour, J. M. J. Org. Chem. 1997, 62, 1376.
12. Huang, S.; Tour, J. M. Tetrahedron Lett. 1999, 40, 3347.
13. (a) Alonso, D. A.; Na´jera, C.; Pacheco, M. C. Org. Lett.
2000, 13, 1823; (b) Miyaura, N.; Suzuki, A. Chem. Rev.
1995, 95, 2457.
NMR (400 MHz, CDCl3) l 8.67 (dd, J=4.4, 1.6 Hz, 2H),
8.27 (br s, 1H), 7.74 (m, 2H), 7.63 (d, J=1.8 Hz, 1H),
7.60 (m, 1H), 7.42 (m, 5H). 13C NMR (100 MHz, CDCl3)
l 149.99, 135.41, 134.65, 132.14, 130.19, 129.61, 128.54,
127.95, 125.50, 122.68, 122.06, 119.15, 99.67, 90.83, 90.27,
84.62. HRMS calcd for C21H12N2O2: 324.0899, found:
324.0897. 14: IR (KBr) 3410.2, 3323.4, 3212.1, 2215.1,
14. Selected spectral data. 2: IR (KBr) 3414.0, 3036.7, 1616.0,
1589.4, 1538.1, 1519.9, 1407.9, 1345.7, 1271.1, 1214.1,
1
828.3 cm−1. H NMR (400 MHz, DMSO-d) l 8.69 (br s,
1627.6, 1592.4, 1548.4, 1511.7, 1410.5, 1331.9 cm−1 1H
.
4H), 8.44 (d, J=1.4 Hz, 1H), 8.04 (1/2 ABqd, J=8.0, 1.4
Hz, 1H), 7.99 (1/2 ABq, J=8.0 Hz, 1H), 7.60 (d, J=5.8
Hz, 2H), 7.57 (d, J=5.8 Hz, 2H). 13C NMR (100 MHz,
DMSO-d) l 150.21, 150.13, 149.42, 136.27, 135.36,
129.16, 129.11, 127.96, 125.50, 125.39, 123.25, 116.55,
94.98, 90.63, 90.59, 88.13. HRMS calcd for C20H11N3O2:
NMR (400 MHz, CDCl3) l 8.64 (br d, J=4.8, 2H), 8.16
(s, 1H), 7.39 (m, 5H), 7.27 (m, 2H), 6.62 (s, 1H), 5.03 (br
s, 2H). 13C NMR (100 MHz, CDCl3) l 151.23, 149.82,
140.65, 138.82, 138.19, 130.49, 128.36, 128.06, 127.52,
125.34, 116.41, 104.85, 93.24, 87.89. HRMS calcd for
C19H13N3O2: 315.1008, found: 315.1011.
.
.