6832
F. Melkonyan et al. / Tetrahedron 67 (2011) 6826e6832
133.1 (JCeF¼33 Hz),141.0,142.1,143.2,164.0; MS m/z (%) 351 (Mþ, 80),
292 (100), 223 (40),121 (90). Anal. Calcd for C17H12F3NO2S: C, 58.11;
H, 3.44; N, 3.99. Found: C, 58.09; H, 3.42; N, 3.98.
Stabile, P.; Laval, G.; Perboni, A. D.; Cimarosti, Z.; Westerduin, P.; Cooke, J. W. B.
Org. Process Res. Dev. 2010, 14, 859e867.
10. For selected reports on the synthesis of 2,3-dihydro-1,4-benzoxazines and
2,3dihydro-1,4-benzothiazines via Cu-catalyzed intramolecular amination re-
actions, see: (a) Minatti, A.; Buchwald, S. L. Org. Lett. 2008, 10, 2721e2724; (b)
Rao, R. K.; Naidu, A. B.; Sekar, G. Org. Lett. 2009, 11, 1923e1926; (c) Prasad, D. J.
C.; Sekar, G. Org. Biomol. Chem. 2009, 7, 5091e5097; (d) Parai, M. K.; Panda, G.
Tetrahedron Lett. 2009, 50, 4703e4705; (e) Bhadra, S.; Adak, L.; Samanta, S.;
4.4.18. Methyl
3-(tert-butylamino)-2-(4-methylphenoxy)acrylate
(7). Reaction of tert-butylamine (219 mg, 3 mmol) and 1b (861 mg,
3 mmol) according to the general procedure afforded 362 mg (46%,
conditions A) or 410 mg (52%, conditions B) of 7, isolated as a yellow
Maidul Islam, A. K. M.; Mukherjee, M.; Ranu, B. C. J. Org. Chem. 20
10, 75,
8533e8541; (f) For the synthesis of 2,3-dihydro-1,4-benzoxazines via a Cu-
catalyzed CeO bond formation, see: Liu, Z.; Chen, Y. Tetrahedron Lett. 2009,
50, 3790e3793; (g) Albanese, D.; Landini, D.; Penso, M.; Scaletti, D. J. Mol. Catal.
A: Chem. 2008, 288, 28e32.
oil. 1H NMR (CDCl3)
d 1.27 (s, 9H), 2.31 (s, 3H), 3.68 (s, 3H), 4.62 (d,
J¼13.8 Hz, 1H), 6.88 (d, J¼8.4 Hz, 2H), 7.09 (d, J¼8.4 Hz, 2H), 7.46 (d,
J¼13.8, 1H). 13C NMR (CDCl3)
d 20.6, 29.0, 50.0, 51.8, 114.7 (2C),
11. Wu, J.-H.; Chang, F.-R.; Hayashi, K.; Shiraki, H.; Liaw, C.-C.; Nakanishi, Y.; Bastow,
K. F.; Yu, D.; Chen, I.-S.; Lee, K.-H. Biorg. Med. Chem. Lett. 2003, 13, 2223e2225.
12. Abdelhamid, A. O.; Elghandor, A. H.; Ahmed, S. A.; Zaki, Y. H. J. Heterocycl. Chem.
2006, 43, 249e254.
13. (a) Bergman, J.; Rosenzweig-Lipson, S.; Spealman, R. D. J. Pharmacol. Exp. Ther.
1995, 273, 40e48; (b) Spealman, R. D. J. Pharmacol. Exp. Ther. 1996, 278,
1128e1137.
14. Rybczynski, P. J.; Zeck, R. E.; Combs, D. W.; Turchi, I.; Burris, T. P.; Xu, J. Z.; Yang,
M.; Demarest, K. T. Biorg. Med. Chem. Lett. 2003, 13, 2359e2362.
15. Rathore, B. S.; Kumar, M. Bioorg. Med. Chem. 2006, 14, 5678e5682.
16. Armenise, D.; De Laurentic, N.; Rosato, A.; Morlacchi, F. J. Heterocycl. Chem.
2006, 43, 1371e1378.
121.0, 128.5 (2C), 129.3, 130.0, 149.8, 161.1; MS m/z (%) 263 (Mþ, 41),
205 (35), 148 (100), 119 (67). Anal. Calcd for C15H21NO3: C, 68.42; H,
8.04; N, 5.32. Found: C, 68.35; H, 8.12; N, 5.38.
References and notes
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problematic under the Cu-catalyzed amination conditions. It was previously
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low yields, whereas no product was observed in the case of six-membered
nitrogen heterocycles. For examples, see; (a) Ref. 3a. (b) van der Hoogen-
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24. Crystallographic data (excluding structure factors) for the structures in this
paper have been deposited with the Cambridge Crystallographic Data Centre.
The CCDC numbers are 720937 (5o) and 720938 (6c). Copies of the data can be
obtained, free of charge, on application to CCDC, 12 Union Road, Cambridge CB2
25. Baliah, V.; Gurumurthy, R. Indian J. Chem., Sect. B: Org. Chem. Incl. Med. Chem.
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2006.
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8. For a review, see; Ilas, J.; Anderluh, P. S.; Dolenc, M. S.; Kikelj, D. Tetrahedron
2005, 61, 7325e7348.
9. For selected reports on the synthesis of 2H-1,4-benzoxazine-3-(4H)-ones via
Cu-catalyzed intramolecular amidation reactions, see: (a) Chen, D.; Shen, G.;
Bao, W. Org. Biomol. Chem. 2009, 7, 4067e4073; (b) Feng, E.; Huang, H.; Zhou,
Y.; Ye, D.; Jiang, H.; Liu, H. J. Org. Chem. 2009, 74, 2846e2849; (c) Giubellina, N.;