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4301
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over NaSO4. After removal of the solvent and lypophiliza-
tion were obtained 1.19 g (85%) 12.
1H NMR (DMSO-d6): d¼0.06 (m, 1H, CH), 0.18 (m, 1H,
CH), 0.40 (m, 2H, CH2), 0.55 (m, 1H, CH), 1.97 (m, 1H,
CH), 2.22 (m, 1H, CH), 2.23 (s, 3H, CH3), 2.7 (m, 2H, CH2),
3.80 (s, 3H, OCH3), 4.68 (d, 1H, J¼15.8 Hz, CH2), 4.77 (m,
1H, CH), 4.82 (d, 1H, J¼15.8 Hz, CH2), 5.18 (‘q’, 1H,
J¼7.5 Hz, CH), 6.80 (‘d’, 1H, J¼8.2 Hz, H arom.), 6.95
(m, 2H, H arom), 7.15 (m, 2H, Harom), 7.30 (m, 5H, Harom),
7.77 (d, 1H, J¼8.2 Hz, Harom), 8.05 (d, 1H, J¼7,5 Hz,
Harom), 8.50 (s, 1H, NH), 8.56 (d, 1H, J¼7.5 Hz, NH), 8.61
(s, 1H, NH), 12.32 (bs, 1H, COOH). MS (ESI): 764.2
[MþH]þ.
10. Lopez, C. A.; Trigo, G. G. Adv. Heterocycl. Chem. 1985, 38,
177.
11. Nefzi, A.; Ostresch, J. M.; Giulianotti, M.; Houghten, R. A.
Tetrahedron Lett. 1998, 39, 8199–8202.
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13. (a) Zeifman, Yu. V.; Gambaryan, N. P.; Knunyants, I. L.
Izvest. Acad. Nauk, SSSR, Ser. Khim. 1965, 2046–2048,
Chem. Abstr. 1966, 64, 6554f. (b) Steglich, W.; Burger, K.;
Du¨rr, M.; Burgis, E. Chem. Ber. 1974, 107, 1488–1498.
(c) Burger, K.; Gaa, K. Chem.-Ztg. 1990, 114, 101–104.
14. (a) Osipov, S. N.; Chkanikov, N. D.; Kolomiets, A. F.; Fokin,
A. F. Izvest. Akad. Nauk, SSSR, Ser. Khim. 1986, 1384–1387,
Acknowledgements
We thank Aventis Pharma Deutschland GmbH, Frankfurt/
Main, and the Fonds of the Chemical Industry for financial
support.
¨
Chem. Abstr. 1987, 106, 156213. (b) Burger, K.; Hoß, E.; Gaa,
K.; Sewald, N.; Schierlinger, C. Z. Naturforsch. B 1991, 46,
361–384. (c) Osipov, S. N.; Golubev, A. S.; Sewald, N.;
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Chem. 1996, 61, 7521–7528.
References and notes
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864–867, Chem. Abstr. 1966, 64, 15861.
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1977, 101, 402–403. (c) Fischer, E. O.; Weiss, K.; Burger, K.
Chem. Ber. 1973, 106, 1581–1588. (d) Burger, K.;
Wucherpfennig, U.; Brunner, E. Fluoro heterocycles with
five-membered rings. Advances in heterocyclic chemistry;
Katritzky, A. R., Ed.; Academic: London, 1994; Vol. 60,
pp 1–64.
3. (a) Toniolo, C.; Benedetti, E. Macromolecules 1991, 24,
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Int. J. Pept. Protein Res. 1988, 32, 544–555.
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1996; pp 42–58 and references cited therein. (c) Koksch, B.;
Sewald, N.; Hofmann, H. J.; Burger, K.; Jakubke, H.-D.
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1993, 65, 149–152.
18. Koksch, B.; Mu¨tze, K.; Osipov, S. N.; Golubev, A. S.; Burger,
K. Tetrahedron Lett. 2000, 41, 3825–3828.
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20. Mu¨tze, K. PhD Thesis, TU Munich, 1993.
21. Kalinowski, H.-O.; Berger, S.; Braun, S. 13C NMR-
spektroskopie; Georg Thieme: Stuttgart, 1984; pp 189–199.
22. Crystallographic data. Crystal system: hexagonal, space
˚
˚
˚
group: P65; a¼10.732(2) A, b¼10.732(2) A, c¼29.534(6) A,
5. (a) Renner, C.; Alefelder, S.; Bae, J. H.; Budisa, N.; Huber, R.;
Moroder, L. Angew. Chem. Int. Ed. 2001, 40, 923–925.
(b) Tang, Y.; Ghirlanda, G.; Vaidehi, N.; Kua, J.; Mainz, T. D.;
Goddard, W. A., III; Degrado, W. F.; Tirrell, D. A.
Biochemistry 2001, 40, 2790–2796. (c) Bilgicer, B.; Fichera,
A.; Kumar, K. J. Am. Chem. Soc. 2001, 123, 4393–4399.
6. Welch, J. T. The effects of selective fluorination on reactivity
in organic and bioorganic chemistry. In Selective fluorination
in organic and bioorganic chemistry. ACS Symposium Series
456; Welch, J. T., Ed.; ACS: Washington DC, 1991; pp 1–15
and references cited therein.
3
˚
a¼b¼908, g¼1208 V¼2945.9(19) A ; Z¼6; density
rcalc¼1.374 g cm23; collected reflection 6399; unique reflec-
tion 2097; number of parameters 251; R1¼0.051; wR2¼0.1267
for [I.2s(I)]. The structure were solved by direct methods
and subsequent Fourier difference techniques and refined
using the program SHELXL-97.28 Further details on the
structure are available on request from Cambridge Crystal-
lographic Data Centre, 12 Union Road, Cambridge, UK on
quoting depository number CCDC 217587.
23. Wehner, V.; Stilz, H. -U.; Burger, K.; Golubev, A.; Osipov,
S. US patent. Pub. No.: US/0183374 2002 A1.
7. Larsson, U.; Carlson, R.; Leroy, J. Acta Chim. Scand. 1993,
47, 380–390.
8. Yoder, C.; Kumar, K. Chem. Soc. Rev. 2002, 31, 335–341.
24. For a review see: Tietze, L. F. Chem. Rev. 1996, 96, 115–136.
25. (a) Burger, K.; Fuchs, A.; Hennig, L.; Helmreich, B.; Greif, D.