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A. Marchetti et al.
LETTER
butylphenolate (0.92 mL of a stock 0.06 M solution in THF)
in THF (18 mL). The resulting orange-brown solution was
stirred at rt for 16 h. The solvent was concentrated in vacuo to
give a solid which used without purification. The solid was
dissolved in CH3CN (15 mL) and the stirred solution was
irradiated at 350 nm with a 300W sunlamp for 21 h. The
solvent was concentrated in vacuo and ether (30 mL) was
added. The black solid which precipitated
The biological activity of compounds 2 and 3, as well as
details of their conformation in solution as determined by
NMR spectroscopy, will be reported in due course.5
Acknowledgement
We warmly thank our colleagues Silvia Pesci and Dr. Daniel Cicero
for recording of the NMR spectra, and Francesca Naimo and Dr.
Fabio Bonelli for the mass spectra.
(RuCp(CH3CN)3PF6) was removed by filtration and washed
with ether (2 x 10 mL). The combined filtrate was
concentrated in vacuo and the residue purified by flash
chromatography (CH2Cl2/MeOH 95:5) to give 10 (11 mg;
37% from 7).
References and Notes
(19) Spectroscopic data for 2: 1H NMR (DMSO-d6, 400 MHz) dH
12.90 (1H, br, COOH), 11.95 (1H, br, COOH), 8.43 (1H, d, J
= 7.8 Hz, NH p-Tyr), 8.34 (1H, d, J = 7.8 Hz, NH Cys), 8.05
(1H, d, J = 5.0 Hz, NH m-Tyr), 7.51 (1H, d, J = 7.7 Hz, arom),
7.30 (1H, t, J = 7.8 Hz, arom), 7.04 (2H, d, J = 7.8 Hz, arom),
6.95 (1H, d, J = 7.7 Hz, arom), 6.92 (1H, d, J = 8.3 Hz, arom),
6.64 (1H, d, J = 8.3 Hz, arom), 6.50 (1H, d, J = 8.6 Hz, NH
Glu), 6.49 (1H, s, arom), 4.60 (1H, t, J = 8.5 Hz, aH p-Tyr),
4.39 (1H, dd, J = 7.2, 11.8 Hz, aH Cys), 4.29 (1H, br d, J = 2.9
Hz, aH m-Tyr), 3.96 (1H, dd, J = 6.0, 12.0 Hz, aH Glu), 3.12-
3.05 (2H, m, bH m-Tyr, bH p-Tyr), 2.96 (1H, dd, J = 10.5,
16.9 Hz, bH p-Tyr), 2.87-2.69 (3H, m, bH m-Tyr, bH Cys),
2.37 (1H, t, J = 8.5 Hz, SH), 2.18-2.01 (2H, m, gH Glu), 1.98
(3H, s, CH3), 1.79-1.74 (1H, m, bH Glu), 1.65-1.58 (1H, m,
bH Glu). MS m/z (IS-MS) 601 (M+ + H, 100), 583 (16), 555
(23), 480 (29), 452 (35).
(1) For a review, see: Kwong, A. D Antiviral Res. 1998, 40, 1-18.
(2) Steinkühler, C.; Biasol, G.; Brunetti, M.; Urbani, A.; Koch,
U.; Cortese, R.; Pessi, A.; De Francesco, R. Biochemistry
1998, 37, 8899. Ingallinella, P.; Altamura, S.; Bianchi, E.;
Taliani, M.; Ingenito, R.; Cortese, R.; De Francesco, R.;
Steinkühler, C.; Pessi, A. Biochemistry 1998, 37, 8906.
(3) Koch, U.; Steinkühler, C.; Cicero, D. O.; Prendergast, K.;
Matassa, V. G.; Pessi, A. manuscript in preparation.
(4) Rich, D. H. In Perspectives in Medicinal Chemistry -
Proceedings of the XIIth International Symposium on
Medicinal Chemistry; Testa, B.; Kyburz, E.; Fuhrer, W.;
Giger, R., Eds.; Verlag Helvetica Chimica Acta: Basel, 1993;
p 15.
(5) Prendergast, K.; Marchetti, A.; Ontoria, J. M.; Cicero, D. O.;
Pesci, S.; Matassa, V. G. manuscript in preparation.
(6) For a review, see: Zhu, J. Synlett 1997, 133.
(7) Janetka, J. W.; Raman, P.; Satyshur, K.; Flentke, G. R.; Rich,
D. H. J. Am. Chem. Soc. 1997, 119, 441.
(8) Pearson, A. J.; Lee, K.; J. Org. Chem. 1994, 59, 2304.
(9) Pearson, A. J.; Park, J. G.; Yang, S. H.; Chuang, Y-H. J.
Chem. Soc., Chem. Commun. 1989, 1363.
(10) Pearson, A. J.; Bignan, G.; Zhang, P.; Chelliah, M. J. Org.
Chem. 1996, 61, 3940.
(11) Janetka, J. W.; Rich, D. H. J. Am. Chem. Soc. 1995, 117,
10585.
(12) Janetka, J. W.; Rich, D. H. J. Am. Chem. Soc. 1997, 119, 6488.
(13) Tong, J. H.; Petitclerc, C.; D’Irorio, A.; Leo Benoiton, N. Can.
J. Biochem. 1971, 49, 877.
(14) Beyermann, M.; Bienert, M.; Niedrich, H.; Carpino, L. A.;
Sadat-Aalee, D. J. Org. Chem. 1990, 55, 721.
(20) Spectroscopic data for 3: 1H NMR (DMSO-d6, 500MHz) dH
12.95 (1H, br, COOH), 12.10 (1H, br, COOH), 8.45 (1H, d, J
= 7.6 Hz, NH, p-Tyr), 8.20 (1H, d, J = 9.9 Hz, NH Cys), 7.97
(1H, d, J = 9.3 Hz, NH Glu), 7.42 (1H, d, J = 7.9 Hz, arom),
7.24 (3H, m, arom and NH m-Tyr), 7.02 (1H, d, J = 7.7 Hz,
arom), 6.97 (1H, d, J = 7.9 Hz, arom), 6.68 (1H, d, J = 7.8 Hz,
arom), 6.57 (1H, d, J = 7.3 Hz, arom), 5.85 (1H, s, arom), 4.69
(1H, br t, J = 9.8 Hz, aH p-Tyr), 4.59 (1H, br s, aH m-Tyr),
4.47 (1H, br d, J = 4.9 Hz, aH Cys), 4.38 (1H, br s, aH Glu),
3.17 (1H, d, J = 10.8 Hz, bH p-Tyr), 3.03 (1H, dd, J = 6.5, 13.9
Hz, bH m-Tyr), 2.96-2.93 (1H, m, bH Cys), 2.87-2.81 (1H, m,
bH Cys), 2.67 (1H, br t, J = 13.2 Hz, bH p-Tyr), 2.22-2.15
(1H, m, gH Glu), 2.09-2.02 (1H, m, gH Glu), 1.91-1.86 (1H,
m, bH Glu ), 1.84 (3H, s, CH3), 1.68-1.63 (1H, m, bH Glu).
MS m/z (IS-MS) 601 (M+ + H, 20), 497 (117), 481 (19), 452
(28), 359 (100), 302 (47).
(15) Moriarty, R. M.; Ku, Y-K.; Gill, U. S. J. Chem. Soc., Chem.
Commun. 1987, 1837.
(16) Gill, T. P.; Mann, K. R. Organometallics 1982, 1, 485.
(17) Pearson, D. A.; Blanchette, M.; Baker, M. L.; Guindon, C. A.
Tetrahedron Lett. 1989, 30, 2739. Triisopropylsilane or
triethylsilane can be used as the cation scavenger.
(18) Experimental procedure for the preparation of 10: A solution
of 9 (48 mg, 0.05 mmol) in THF (6 mL) was added over 4.3 h
by syringe pump to a solution of sodium 2,6-di-tert-
Article Identifier:
1437-2096,E;1999,0,S1,1000,1002,ftx,en;W08999ST.pdf
Synlett 1999, S1, 1000–1002 ISSN 0936-5214 © Thieme Stuttgart · New York