4120
C. Lamberth et al. / Tetrahedron Letters 53 (2012) 4117–4120
M.; Haleen, S. J.; Keiser, J. A.; Flynn, M. A.; Welch, K. M.; Hallak, H.; Taylor, D. G.;
Reynolds, E. E. J. Med. Chem. 1995, 38, 1259–1263.
16. Representative
procedure
for
the
synthesis
of
fully
substituted
c
-hydroxybutenolides: DBU (1.1 g, 7.3 mmol) was added dropwise to
a
2. Black, W. C.; Brideau, C.; Chan, C.-C.; Charleson, S.; Cromlish, W.; Gordon, R.;
Grimm, E. L.; Hughes, G.; Leger, S.; Li, C.-S.; Riendeau, D.; Therien, M.; Wang, Z.;
Xu, L.-J.; Prasit, P. Bioorg. Med. Chem. Lett. 2003, 13, 1195–1198.
3. Hasegawa, T.; Yamada, K.; Shigemori, H.; Hasegava, K.; Miyamoto, K.; Ueda, J.
Plant Growth Regul. 2002, 37, 45–47.
4. Surmont, R.; Verniest, G.; De Kimpe, N. J. Org. Chem. 2010, 75, 5750–5753.
5. Lamberth, C.; Trah, S.; Wendeborn, S.; Dumeunier, R.; Courbot, M.; Godwin, J.;
Schneiter, P. Bioorg. Med. Chem. 2012, 20, 2803–2810.
6. Mederski, W. W. K. R.; Osswald, M.; Dorsch, D.; Anzali, S.; Christadler, M.;
Schmitges, C.-J.; Wilm, C. Bioorg. Med. Chem. Lett. 1998, 8, 17–22.
7. (a) Borate, H. B.; Sawargave, S. P.; Chavan, S. P.; Chandavarkar, M. A.; Iyer, R.;
Tawte, A.; Rao, D.; Deore, J. V.; Kudale, A. S.; Mahajan, P. S.; Kangire, G. S. Bioorg.
Med. Chem. Lett. 2011, 21, 4873–4878; (b) Pattabiraman, V. R.; Padakanti, S.;
Veeramaneni, V. R.; Pal, M.; Yeleswarapu, K. R. Synlett 2002, 947–951; (c)
Padakanti, S.; Veeramaneni, V. R.; Pattabiraman, V. R.; Pal, M.; Yeleswarapu, K.
R. Tetrahedron Lett. 2002, 43, 8715–8719.
solution of 4-ethynylbenzyl methyl ketone (26, 0.8 g, 4.8 mmol) in 3 ml of
N,N-dimethylformamide at 0 °C under an argon atmosphere. The mixture
was stirred for further 15 min at 0 °C, then
a solution of ethyl 2,4,6-
trifluorophenylglyoxylate (23, 1.3 g, 5.3 mmol) in 3 ml of N,N-dimethyl-
formamide was added very slowly and the reaction mixture was kept for
12 h at 0 °C. Subsequently it was quenched by addition of 2 ml of ethanol and
3.5 ml of 4 M aqueous sodium hydroxide, then the obtained solution was
stirred for 15 min and washed with diethyl ether. The aqueous phase was
acidified to pH 1 with concentrated aqueous hydrochloride acid and extracted
with diethyl ether. The organic layer was dried over sodium sulfate and
purified by chromatography on silica gel to obtain 4-(4-ethynylphenyl)-5-
hydroxy-5-methyl-3-(2,4,6-trifluorophenyl)-5H-furan-2-one
(27,
0.6 g,
1.9 mmol, 39%); mp 186–188 °C. 1H NMR (400 MHz, CDCl3): d (ppm) = 1.71
(s, 3H), 3.24 (s, 1H), 6.67 (t, 1H), 6.82 (t, 1H), 7.43 (d, 2H), 7.51 (d, 2H). LC-MS:
tR = 1.83 min, m/z = 345 [M+1].
17. Further spectroscopic data:
8. McEvoy, F. J.; Allen, G. R. J. Med. Chem. 1974, 17, 281–286.
9. Liu, P.; Lanza, T. J.; Jewell, J. P.; Jones, C. P.; Hagmann, W. K.; Lin, L. S.
Tetrahedron Lett. 2003, 44, 8869–8871.
Compound 20: 1H NMR (400 MHz, CDCl3): d (ppm) = 1.84 (s, 3H), 3.97 (s, 3H),
6.70 (t, 1H), 6.76 (d, 1H), 6.85 (t, 1H), 7.82 (dd, 1H), 8.40 (d, 1H). LC–MS:
tR = 1.69 min, m/z = 352 [M+1].
10. Dumeunier, R.; Lamberth, C.; Trah, S. (Syngenta AG), PCT application WO 2009/
127612, Priority 14.4.2008, Publication 22.10.2009.
11. (a) Tang, X.-Y.; Shi, M. Tetrahedron 2009, 65, 9336–9343; (b) Yang, Y.-H.; Shi, M.
Org. Lett. 2006, 8, 1709–1712; (c) Yang, Y.-H.; Shi, M. Eur. J. Org. Chem. 2006,
5394–5403.
12. Armstrong, A.; Critchley, T. J.; Gourdel-Martin, M.-E.; Kelsey, R. D.; Mortlock, A.
A. J. Chem. Soc., Perkin Trans. 1 2002, 1344–1350.
13. Ueno, T.; Oikawa, M.; Oikawa, H.; Ichihara, A. Biosci. Biotech. Biochem. 1995, 59,
2104–2110.
14. (a) Li, L.; Chen, H.; Lin, Y. Synth. Commun. 2007, 37, 985–991; (b) Molinaro, C.;
Mowat, J.; Gosselin, F.; O’Shea, P. D.; Marcoux, J.-F.; Angelaud, R.; Davies, I. W. J.
Org. Chem. 2007, 72, 1856–1858.
15. (a) Lai, G.-Q.; Liu, S.-L.; Xu, J.-F.; Shen, Y.-J. J. Chem. Res. 2006, 203–204; (b)
Rodriguez, J. G.; Esquivias, J.; Lafuente, A.; Rubio, L. Tetrahedron 2006, 62,
3112–3122.
Compound 30a: 1H NMR (400 MHz, CDCl3): d (ppm) = 0.69–0.76 (m, 3H), 0.85
(t, 1H), 1.08 (d, 1H), 1.19–1.27 (m, 3H), 1.64 (s, 3H), 2.25 (q, 1H), 4.36 (br s, 1H),
7.31–7.40 (m, 2H), 7.52 (s, 1H). LC–MS: tR = 1.85 min, m/z = 315 [M+1].
Compound 30b: 1H NMR (400 MHz, CDCl3): d (ppm) = 0.93–0.98 (m, 1H), 1.20
(d, 1H), 1.31 (t, 1H), 1.62–1.69 (m, 1H), 2.26 (q, 1H), 6.97 (t, 2H), 7.06–7.38 (m,
3H), 7.75 (dd, 1H), 8.11 (t, 1H), 16.57 (br s, 1H). LC–MS: tR = 1.50 min, m/z = 317
[M+1].
Compound 30c: 1H NMR (400 MHz, CDCl3): d (ppm) = 1.12 (t, 3H), 2.48 (s, 3H),
4.19 (q, 2H), 6.65 (d, 1H), 7.12 (br s, 1H), 7.34–7.50 (m, 6H). LC–MS:
tR = 1.46 min, m/z = 345 [M+1], 300 [MÀOEt].
Compound 30d: 1H NMR (400 MHz, CDCl3): d (ppm) = 2.19 (s, 3H), 4.07 (br s,
1H), 6.98–7.07 (m, 3H), 7.10 (d, 2H), 7.16 (t, 1H), 7.28–7.43 (m, 5H), 7.69 (t,
1H). LC–MS: tR = 1.92 min, m/z = 395 [M+1].