Y. Hu et al. / Tetrahedron 67 (2011) 7258e7262
7261
J¼8.0 Hz, 2H); 13C NMR (100 MHz, CDCl3)
d
20.5, 70.0, 110.9, 125.3,
137.0, 152.0, 161.6, 162.6. HRMS (ESI) calcd for C20H13F6O2 (MþH),
125.8, 128.9, 141.5, 162.9, 173.1.
399.0820; found, 399.0792.
4.1.15. 4-(2-Methoxy phenyl)furan-2(5H)-one (3o)12
(400 MHz, CDCl3) 3.84 (s, 3H), 5.16 (s, 2H), 6.46 (s, 1H), 6.92e6.97
(m, 2H), 7.32e7.39 (m, 2H); 13C NMR (100 MHz, CDCl3)
111.7, 114.8, 118.7, 120.9, 128.3, 132.9, 158.4, 161.0, 174.7.
.
1H NMR
4.2.6. 6-Methyl-3,4-bis(4-methylbenzoatyl)-2H-pyran-2-one
d
(3w). 1H NMR (400 MHz, CDCl3)
d
2.36 (s, 3H), 3.88 (s, 6H), 6.20 (s,
1H), 7.15 (d, J¼8.0 Hz, 2H), 7.21 (d, J¼8.0 Hz, 2H), 7.87e7.90 (m, 4H);
13C NMR (100 MHz, CDCl3)
20.0, 52.1, 52.2, 106.6, 121.5, 128.6,
d
55.5, 72.7,
d
129.2, 129.3, 129.6, 130.4, 130.9, 138.3, 141.5, 152.4, 161.3, 162.6,
166.2, 166.6. HRMS (ESI) calcd for C22H19O6 (MþH), 379.1182;
found, 379.1156.
4.1.16. 4-(4-Methoxy phenyl)furan-2(5H)-one (3p)12
.
1H NMR
(400 MHz, CDCl3)
d 3.79 (s, 3H), 5.13 (s, 2H), 6.18 (s, 1H), 6.90 (d,
J¼8.0 Hz, 2H), 7.39 (d, J¼8.0 Hz, 2H); 13C NMR (100 MHz, CDCl3)
d
55.5, 70.9, 110.5, 114.6, 122.2, 128.2, 162.3, 163.5, 174.3.
Acknowledgements
4.1.17. 4-(4-(Dimethylamino)phenyl)furan-2(5H)-one
(3q)17 1H
.
Financial support from the National Natural Science Foundation
of China (Nos. 20862009 and 20962010) and the Natural Science
Foundation of Jiangxi Province (No. 2008GQH0026) is gratefully
acknowledged.
NMR (400 MHz, CDCl3)
d 3.06 (s, 6H), 5.18 (s, 2H), 6.11 (s, 1H), 6.69
(d, J¼8.0 Hz, 2H), 7.37 (d, J¼8.0 Hz, 2H); 13C NMR (100 MHz, CDCl3)
d
40.0, 70.9, 107.4, 111.6, 118.7, 128.0, 152.4, 164.2, 177.6.
4.2. General experimental procedure for palladium-catalyzed
cross-coupling reactions of 3-bromo-4-hydroxy-2-pyrone
with arylboronic acids
Supplementary data
Supplementary data associated with this article can be found in
clude MOL files and InChiKeys of the most important compounds
described in this article.
A solution of 3-bromo-4-hydroxy-6-methyl-2H-pyran-2-one 1d
(0.3 mmol), p-toluenesulfonyl chloride (0.33 mmol, 1.1 equiv),
K2HPO4$3H2O (0.9 mmol, 3.0 equiv), Pd(OAc)2 (5 mol %), PCy3
(10 mol %), and ArB(OH)2 (0.75 mmol, 2.5 equiv) in methanol
(4.0 mL) was stirred at 60 ꢀC for a period of time. After completion
of reaction as indicated by TLC, the reaction was quenched by the
addition of saturated aqueous NH4Cl (5.0 mL), and the mixture was
extracted with EtOAc (4.0 mLꢁ3). The combined organic layer was
dried over Na2SO4 and concentrated in vacuo. The residue was
purified by column chromatography on silica gel to provide the
desired product 3.
References and notes
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T.; Besl, H.; Bross, M.; Herrmann, R.; Mocek, U.; Steffan, B.; Steglich, W. J. An-
tiobiot. 1990, 43, 1413; (i) For (ꢂ)-dysiolide, see: Gunaskera, G. P.; McCarthy, P. J.;
Borges, M. K.; Lobkovsky, E.; Clardy, J. J. Am. Chem. Soc. 1996, 118, 8759; (j)
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references cited therein.
4.2.1. 6-Methyl-3,4-diphenyl-2H-pyran-2-one
(3r)18
.
1H
NMR
(400 MHz, CDCl3)
d
2.25 (s, 3H), 6.09 (s, 1H), 7.00 (d, J¼8.0 Hz, 4H),
7.13 (d, J¼8.0 Hz, 6H); 13C NMR (100 MHz, CDCl3)
d 19.9,107.1, 122.0,
127.5, 127.9, 128.2, 128.6, 130.8, 133.8, 137.5, 152.7, 160.1.
4.2.2. 6-Methyl-3,4-di-m-tolyl-2H-pyran-2-one
(400 MHz, CDCl3) 2.23 (s, 6H), 2.31 (s, 3H), 6.16 (s, 1H), 6.82e6.88
(m, 2H), 6.93 (s, 1H), 7.00e7.07 (m, 5H); 13C NMR (100 MHz, CDCl3)
19.9, 21.3, 21.4, 107.1, 122.0, 125.8, 127.8, 127.8, 128.0, 128.3, 129.2,
(3s). 1H
NMR
d
d
129.3, 131.3, 133.8, 137.3, 137.4, 137.8, 152.7, 159.8, 163.7. HRMS (ESI)
calcd for C20H19O2 (MþHþ) 291.1385; found, 291.1354.
4.2.3. 6-Methyl-3,4-di-p-tolyl-2H-pyran-2-one
(3t). 1H
NMR
(400 MHz, CDCl3)
d
2.29 (s, 6H), 2.30 (s, 3H), 6.14 (s,1H), 6.98 (d, J¼8
4. (a) Hayashi, Y.; Yuki, Y.; Matsumoto, T. Tetrahedron Lett. 1977, 41, 3637; (b) Chen,
K. K.; Kovarikova, A. J. Pharm. Sci. 1967, 56, 1535; (c) Kupchan, S. M.; Moniot, J. L.;
Sigel, C. W.; Hemingway, R. J. J. Org. Chem. 1971, 36, 2611; (d) For a synthesized
0.0 Hz, 4H), 7.02 (t, J¼5.2 Hz, 3H); 13C NMR (100 MHz, CDCl3)
d 19.2,
19.8, 21.2, 107.2, 121.6, 128.6, 128.7, 128.9, 130.6, 130.9, 131.0, 134.7,
137.1, 138.6, 152.2, 159.6, 163.8, HRMS (ESI) calcd for C20H19O2
(MþH), 291.1385; found, 291.1346.
a
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Domagala, J. M.; Humblet, C.; Bhat, T. N.; Liu, B.; Guenin, D. M. A.; Baldwin, E. T.;
Erickson, J. W.; Sawyer, T. K. J. Am. Chem. Soc. 1994, 116, 6989; (e) Sunazuka, T.;
Handa, M.; Nagai, K.; Shirahata, T.; Harigaya, Y.; Otoguro, K.; Kuwajima, I.;
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Liao, C.-C. Org. Lett. 2000, 2, 2049.
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Hattori, Y.; Tanaka, A.; Oritani, T. Org. Lett. 2002, 4, 1083; (d) Chio, Y.; Choo, H.;
Chong, Y.; Lee, S.; Olgen, S.; Schinazi, R. F.; Chu, C. K. Org. Lett. 2002, 4, 305; (e)
Roush, W. R.; Limberakis, C.; Kunz, R. K.; Barda, D. A. Org. Lett. 2002, 4, 1543; (f)
Ghosh, N.; McKee, S. P.; Thompson, W. J.; Darke, P. L.; Zugory, J. C. J. Org. Chem.
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6. (a) Beccalli, E. M.; Broggini, G.; Martinelli, M.; Sottocornola, S. Chem. Rev. 2007,
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4.2.4. 3,4-Bis(4-methoxyphenyl)-6-methyl-2H-pyran-2-one (3u). 1H
NMR (400 MHz, CDCl3)
6.65e6.70 (m, 4H), 6.95e7.01 (m, 4H); 13C NMR (100 MHz, CDCl3)
19.8, 55.1, 55.2, 107.1, 113.6, 113.7, 120.7, 126.4, 129.8, 130.3, 132.0,
d 2.22 (s, 3H), 3.67 (s, 6H), 6.07 (s, 1H),
d
151.7, 158.8, 159.4, 159.8, 163.9, HRMS (ESI) calcd for C20H19O4
(MþH), 323.1283; found, 323.1285.
4.2.5. 6-Methyl-3,4-bis(4-(trifluoromethyl)phenyl)-2H-pyran-2-one
(3v). 1H NMR (400 MHz, CDCl3)
d 2.37 (s, 3H), 6.18 (s, 1H), 7.21 (d,
J¼8.0 Hz, 2H), 7.26 (d, J¼8.0 Hz, 2H), 7.49e7.54 (m, 4H); 13C NMR
(100 MHz, CDCl3)
d 20.0, 106.6, 121.2, 122.2, 124.9, 125.1, 125.5,
127.4, 127.6, 127.9, 128.9, 129.4, 129.7, 130.1, 130.4, 130.9, 131.2, 131.5,