7
2
4%). Colourless oil; 74% yield; IR (film) υmax 3417, 2938,
Tudzynski, P. and Delen, N., Eds.; Springer Netherlands:
Dordrecht, The Netherlands, 2007; pp 163-179.
12. Choquer, M.; Fournier, E.; Kunz, C.; Levis, C.; Pradier, J.; Simon,
A.; Viaud, M. FEMS Microbiol. Lett. 2007, 277, 1.
3. Collado, I. G.; Macias-Sanchez, A. J.; Hanson, J.R. Nat. Prod.
Rep. 2007, 24, 674 and references cited therein.
4. Bradshaw, A. P. W.; Hanson, J. R.; Nyfeler, R.; Sadler, I. H. J.
Chem. Soc., Perkin Trans. 1 1982, 2187.
15. Siewers, V.; Viaud, M.; Jimenez-Teja, D.; Collado, I. G.; Schulze
Gronover, C.; Pradier, J. M.; Tudzynsk, B.; Tudzynski, P. Mol.
Plant-Microbe Interact. 2005, 18, 602.
16. Pinedo, C.; Wang, C. M.; Pradier, J. M.; Dalmais, B.; Choquer,
M.; Le Pêcheur, P.; Morgant, G.; Collado, I. G.; Cane, D. E.;
Viaud, M. l. ACS Chem. Biol. 2008, 3, 791.
-
1 1
3
854, 1732, 1604, 1512, 1223, 1023 cm ; H NMR (CDCl , 400
1
3
MHz) (see Table 4); C NMR (CDCl3, 100 MHz) (see Table S4
+
+
of the SI); HRMS (CI ): m/z 240.0805 [M] (calcd for C12
40.0798).
4
H13FO ,
1
2
1
(
4R,6S)-4-hydroxy-6-((R)-1-phenylethoxy)tetrahydro-2H-
pyran-2-one (19a). (170 mg, 72%). Colourless oil; HPLC t = 38
min (Petroleum ether : ethyl acetate 60:40; flow = 3.5 mL/min);
R
2
0
[
α]
D
+215.0 (c 0.5, CHCl ); IR (film) υmax 3398, 2927, 2857,
3
-1 1
1
752, 1560, 1229, 1024 cm ; H NMR (CDCl
3
, 400 MHz) (see
, 100 MHz) (see Table S4 of the SI);
1
3
Table 4); C NMR (CDCl
HRMS (CI ): m/z 221.0818 [M-CH
2
3
+
+
3
]
(calcd for C12
H
13
O ,
4
17. Wang, C. M.; Hopson, R.; Lin, X.; Cane, D. E. J. Am. Chem. Soc.
2009, 131, 8360.
8. Shiina, I.; Fukui, H. Chem. Commun. 2009, 385-400.
21.0814).
1
4.3.6. Preparation of (4S,6S)-4-hydroxy-6-((R)-1-
phenylethoxy)tetrahydro-2H-pyran-2-one (19b).
19. Reino, J. L.; Durán-Patrón, R. M.; Daoubi, M.; Collado, I. G.;
4
1
Hernández-Galán, R. J. Org. Chem. 2006, 71, 562-565.
2
0. Massaroli, M.; Moraga, J.; Bastos Borges, K.; Ramírez-Fernández,
J.; Viaud, M.; González Collado, I.; Durán-Patrón, R.; Hernández-
Galán, R. ChemBioChem 2013, 14, 132-136.
1.0 M tetrabutylammonium fluoride (TBAF) (0.6 mmol) in
THF was added dropwise to a solution of the corresponding
tetrahydro-2H-pyran-2-one 3b (0.05 mmol) and acetic acid (0.5
mmol) in dry THF (0.6 mL) under an argon atmosphere at room
temperature. The reaction was stirred for 16 h and brine (10 mL)
was then added. The aqueous phase was extracted with ethyl
acetate (3x20 mL), dried over anhydrous sodium sulfate and
filtered. Evaporation of the solvent gave a crude product that was
purified by silica gel column chromatography (petroleum ether /
EtOAc, 80:20), to afford the corresponding deprotected
tetrahydro-2H-pyran-2-one 19b (8.5 mg, 72%) as a colorless oil;
21. Dalmais, B.; Schumacher, J.; Moraga, J.; Le Pêcheur, P.;
Tudzynski, B.; Collado, I. G.; Viaud, M. Molecular Plant
Pathology 2011, 12, 564-579.
2
2. Heller, J.; Ruhnke, N.; Espino, J. J.; Massaroli, M.; Collado, I. G.;
Tudzynski, P. Molecular Plant-Microbe Interactions 2012, 25,
8
02-816.
23. Amselem, J.; Cuomo, C. A.; van Kan, J. A. L.; Viaud, M.; Benito,
E. P.; Couloux, A.; Coutinho, P. M.; de Vries, R. P.; Dyer, P. S.;
Fillinger, S.; Fournier, E.; Gout, L.; Hahn, M.; Kohn, L.; Lapalu,
N.; Plummer, K. M.; Pradier, J. M.; Quévillon, E.; Sharon, A.;
Simon, A.; Have, A.; Tudzynski, B.; Tudzynski, P.; Wincker, P.;
Andrew, M.; Anthouard, V.; Beever, R. E.; Beffa, R.; Benoit, I.;
Bouzid, O.; Brault, B.; Chen, Z.; Choquer, M.; Collémare, J.;
Cotton, P.; Danchin, E. G.; Da Silva, C.; Gautier, A.; Giraud, C.;
Giraud, T.; Gonzalez, C.; Grossetete, S.; Güldener, U.; Henrissat,
B.; Howlett, B. J.; Kodira, C.; Kretschmer, M.; Lappartient, A.;
Leroch, M.; Levis, C.; Mauceli, E.; Neuvéglise, C.; Oeser, B.;
Pearson, M.; Poulain, J.; Poussereau, N.; Quesneville, H.; Rascle,
C.; Schumacher, J.; Ségurens, B.; Sexton, A.; Silva, E.; Sirven, C.;
Soanes, D. M.; Talbot, N. J.; Templeton, M.; Yandava, C.;
Yarden, O.; Zeng, Q.; Rollins, J. A.; Lebrun, M. H. ; Dickman, M.
PLoS Genetics 2011, 7, e1002230.
HPLC t
R
= 47 min (Petroleum ether : ethyl acetate 60:40; flow =
2
0
3
.5 mL/min); [α]
D
+130.0 (c 0.1, CHCl ); IR (film) υmax 3412,
3
-1 1
2
927, 2857, 1752, 1560, 1229, 1024 cm ; H NMR (CDCl3, 400
13
MHz) (see Table 4); C NMR (CDCl , 100 MHz) (see Table S4
of the SI); HRMS (CI ): m/z 221.0817 [M-CH
3
+
+
3
] (calcd for
12 13 4
C H O
, 221.0814).
Acknowledgments
This research was supported by grants from Junta de
Andalucía (P07-FQM-02925) and, in part, from MINECO
2
4. Ascari, J.; Boaventura, M. A. D.; Takahashi, J. A.; Duran-Patron,
R.; Hernandez-Galan, R.; Macias-Sanchez, A. J.; Collado, I. G. J.
Nat. Prod. 2013, 76, 1016 and references cited therein.
(
AGL2012-39798-C02-01) (Spain). A. J. M. S. gratefully
acknowledges a RSC research fund grant (UK). J. M. B. thanks
Junta de Andalucía for Research Fellowship. Use of NMR and
mass spectrometry (QTOF) facilities at Servicio Centralizado de
Ciencia y Tecnología (SCCYT) of the University of Cádiz is
acknowledged.
25. Endo, A. Nat. Med. (N. Y., NY, U. S.) 2008, 14, 1050.
26. Endo, A. Proc. Jpn. Acad., Ser. B. 2010, 86, 484.
2
2
2
3
3
7. Salakhutdinov, N. F.; Laev, S. S. Bioorg. Med. Chem. 2014, 22,
551.
8. Jain, K. S.; Kathiravan, M. K.; Somani, R. S.; Shishoo, C. J.
Bioorg. Med. Chem. 2007, 15, 4674.
3
9. Macreadie, I. G.; Johnson, G.; Schlosser, T.; Macreadie, P. I.
FEMS Microbiol. Lett. 2006, 262, 9.
0. Cazar, M. E.; Schmeda-Hirschmann, G.; Astudillo, L. World J.
Microbiol. Biotechnol. 2005, 21, 1067-1075.
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2
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1
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