860 Journal of Natural Products, 2009, Vol. 72, No. 5
Barancelli et al.
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5.99-5.92 (m, 1H), 3.67 (t, J ) 6.2 Hz, 2H), 2.61 (t, J ) 7.4 Hz, 2H),
2.39-2.16 (m, 5H), 1.75-1.54 (m, 6H), 1.39-1.19 (m, 16H); 13C NMR
(CDCl3, 100 MHz) δ 156.6, 140.5, 109.9, 104.4, 77.6, 76.8, 65.6, 65.1,
62.1, 31.6, 29.4, 29.4, 29.3, 29.2, 29.0, 28.9, 28.7, 28.2, 27.9, 27.8,
24.5, 19.0, 18.9; MS (EI, 70 eV) m/z (relative intensity) 342 (1), 310
(5), 156 (22), 130 (29), 94 (53), 80 (100), 66 (19); anal. (%) calc for
C23H34O2, C 80.65, H 10.01, found C 80.44, H 9.78.
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Synthesis of 19-Furan-2-ylnonadeca-5,7-diynoic Acid (1).18 Py-
ridinium dichromate (PDC) (0.66 g, 1.75 mmol) was added to the
solution of alcohol 11 (0.17 g, 0.5 mmol) in DMF (1 mL). The mixture
was stirred for 4 h and poured into H2O. The product was extracted
with Et2O (3×). The organic extract was washed successively with
H2O and dilute HCl solution and dried over MgSO4, and the solvent
removed under reduced pressure using a rotary evaporator. The residue
was purified by column chromatography on silica gel using EtOAc/n-
1
hexane (40:60) as eluent: yield 0.872 g (49%); H NMR (CDCl3, 400
MHz) δ 7.30-7.27 (m, 1H), 6.30-6.23 (m, 1H), 5.99-5.93 (m, 1H),
2.60 (t, J ) 7.5 Hz, 2H), 2.49 (t, J ) 7.4 Hz, 2H), 2.35 (t, J ) 6.9 Hz,
2H), 2.24 (t, J ) 7.0 Hz, 2H), 1.84 (quint, J ) 7.1 Hz, 2H), 1.62 (quint,
J ) 7.1 Hz, 2H), 1.51 (quint, J ) 7.3 Hz, 2H), 1.35-1.23 (m, 14H);
13C NMR (CDCl3, 50 MHz) δ 179.1, 156.5, 140.5, 109.9, 104.4, 78.0,
75.6, 66.3, 64.9, 32.5, 29.5, 29.4, 29.4, 29.3, 29.1, 29.0, 28.7, 28.2,
27.9, 27.9, 23.1, 19.1, 18.5; IR (KBr) (νmax, cm-1) 3446-2370, 2918,
2846, 2150, 1690, 1598, 1508, 1463, 1443, 1412, 1205, 1180, 1009,
885; anal. (%) calc for C23H32O3, C 77.49, H 9.05, found C 77.82, H
8.83.
Synthesis of 19-Furan-2-ylnonadeca-5,7-diynoic Acid Methyl
Ester (2).19 To a solution of 1 (0,178 g, 0.5 mmol) in absolute MeOH
(1 mL) was added 0.03 mL of SOCl2. The mixture was stirred at room
temperature for 15 h, and the solvent was removed in vacuo. The residue
was purified by column chromatography on silica gel using EtOAc/n-
1
hexane (20:80) as eluent: yield 0.121 g (65%); H NMR (CDCl3, 200
MHz) δ 7.30-7.27 (m, 1H), 6.29-6.25 (m, 1H), 5.98-5.94 (m, 1H),
3.67 (s, 3H), 2.60 (t, J ) 7.5 Hz, 2H), 2.44 (t, J ) 7.3 Hz, 2H), 2.33
(t, J ) 6.8 Hz, 2H), 2.23 (t, J ) 7.0 Hz, 2H), 1.84 (quint, J ) 7.0 Hz,
2H), 1.62 (quint, J ) 7.3 Hz, 2H), 1.50 (quint, J ) 7.3 Hz, 2H),
1.34-1.22 (m, 14H); 13C NMR (CDCl3, 50 MHz) δ 173.3, 156.5, 140.5,
109.9, 104.4, 77.9, 75.8, 66.2, 65.0, 51.5, 32.6, 29.4, 29.4, 29.3, 29.2,
29.1, 29.0, 28.7, 28.2, 27.9, 27.9, 23.4, 19.1, 18.6; IR (neat) (νmax, cm-1
)
3462, 3115, 2924, 2852, 2256, 2164, 1597, 1506, 1462, 1435, 1159,
1148, 1074, 1074, 1107, 885; anal. (%) calc for C24H34O3, C 77.80, H
9.25, found C 77.52, H 8.79.
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A. L.; Silveira, C. C.; Stefani, H. A.; Rocha, J. B. T. Tetrahedron
Lett. 2001, 42, 8927.
Acknowledgment. We are grateful to Conselho Nacional de
Desenvolvimento Cient´ıfico e Tecnolo´gico, Coordenac¸a˜o de Aperfe-
ic¸oamento de Pessoal de N´ıvel Superior (SAUX) and Fundac¸a˜o de
Amparo a` Pesquisa do Estado do Rio Grande do Sul, for the fellowship
and financial support.
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Patterson, S.; Ridenour, S.; Schmidt, M.; Smith, E.; Wells, A. J. Synlett
2004, 1339.
(16) Since the use of Cadiot-Chodkiewicz classical conditions led to a
lower yield of cross-coupling product, we carried out the reaction under
Alami’s improved conditions.17
Supporting Information Available: Experimental procedures,
additional experimental details for the preparation of all compounds,
and 1H and 13C NMR spectra for all reaction products. This material is
(17) Alami, M.; Ferri, F. Tetrahedron Lett. 1996, 37, 2763.
(18) Corey, E. J.; Schmidt, G. Tetrahedron Lett. 1979, 5, 399.
(19) Kazemi, F.; Kiasat, A. R.; Mombaini, B. Phosphorus, Sulfur, Silicon
Relat. Elem. 2004, 179, 1187.
References and Notes
(1) (a) Senn, M.; Gunzenhauser, S.; Brun, R.; Se´quin, U. J. Nat. Prod.
2007, 70, 1565. (b) Tian, Y.; Wei, X.; Xu, H. J. Nat. Prod. 2006, 69,
1241. (c) Parish, C. A.; Huber, J.; Baxter, J.; Gonzalez, A.; Collado,
(20) Abrams, S. R. Can. J. Chem. 1984, 62, 1333.
NP9000637