PAPER
Novel Synthetic Strategy of N-Arylated Heterocycles
2533
EI–MS: m/z = 315 [M].
(2) For reviews, see: (a) Wolfe, J. P.; Wagaw, S.; Marcoux, J.-
F.; Buchwald, S. L. Acc. Chem. Res. 1998, 31, 805.
(b) Hartwig, J. F. Angew. Chem. Int. Ed. 1998, 37, 2046.
(c) Yang, B. H.; Buchwald, S. L. J. Organomet. Chem. 1999,
576, 125. (d) Muci, A. R.; Buchwald, S. L. Practical
Palladium Catalysts for C–N and C–O Bond Formation, In
Cross-Coupling Reaction: A Practical Guide, Topics in
Current Chemistry Ser. 219; Miyaura, N., Ed.; Springer-
Verlag: New York, 2002.
Anal. Calcd for C21H17NO2: C, 79.98; H, 5.43; N, 4.44; O, 10.15.
Found: C, 79.86; H, 5.58; N, 4.21.
5-Phenyl-2,3,4,5-tetrahydro-1,5-benzoxazepine (5q)
Yield: 51%; yellow oil.
IR (KBr): 3058, 2941, 2868, 1588, 1488, 1362, 1289, 1241, 1197,
1062, 744, 690 cm–1.
1H NMR (400 MHz, CDCl3): d = 7.27–7.14 (m, 4 H), 7.07–6.95 (m,
2 H), 6.93–6.82 (m, 3 H), 4.01 (t, J = 5.8 Hz, 2 H), 3.90 (t, J = 6.2
Hz, 2 H), 2.16–2.03 (m, 2 H).
13C NMR (100 MHz, CDCl3): d = 158.6, 154.1, 147.8, 129.4, 130.1,
129.4, 129.3, 127.5, 121.4, 120.9, 120.6, 115.2, 114.3, 65.9, 48.7,
27.2.
(3) (a) Wolfe, J. P.; Buchwald, S. L. J. Am. Chem. Soc. 1997,
119, 6054. (b) Brenner, E.; Fort, Y. Tetrahedron Lett. 1998,
39, 5359. (c) Brenner, E.; Schneider, R.; Fort, Y.
Tetrahedron 1999, 55, 12829. (d) Desmarets, C.; Schneider,
R.; Fort, Y. Tetrahedron Lett. 2000, 41, 2875. (e) Brenner,
E.; Schneider, R.; Fort, Y. Tetrahedron Lett. 2000, 41, 288.
(f) Lipshutz, B. H.; Ueda, H. Angew. Chem. Int. Ed. 2000,
39, 4492. (g) Desmarets, C.; Schneider, R.; Fort, Y.
Tetrahedron Lett. 2001, 42, 247. (h) Desmarets, C.;
Schneider, R.; Fort, Y. Tetrahedron 2001, 57, 7657.
(i) Brenner, E.; Schneider, R.; Fort, Y. Tetrahedron 2002,
58, 6913. (j) Desmarets, C.; Schneider, R.; Fort, Y.;
Walcarius, A. J. Chem. Soc., Perkin Trans. 2 2002, 1844.
(k) Lipshutz, B. H.; Tasler, S.; Chrisman, W.; Spliethoff, B.;
Tesche, B. J. Org. Chem. 2003, 68, 1177. (l) Tasler, S.;
Lipshutz, B. H. J. Org. Chem. 2003, 68, 1190.
(4) (a) Wolfe, J. P.; Rennels, R. A.; Buchwald, S. L.
Tetrahedron 1996, 52, 7525. (b) Peat, A. J.; Buchwald, S. L.
J. Am. Chem. Soc. 1996, 118, 1028. (c) Wagaw, S.;
Rennels, R. A.; Buchwald, S. L. J. Am. Chem. Soc. 1997,
119, 8451. (d) He, F.; Foxman, B. M.; Snider, B. B. J. Am.
Chem. Soc. 1998, 120, 6417. (e) Abouabdellah, A.; Dodd,
R. H. Tetrahedron Lett. 1998, 39, 2119. (f) Yang, B. H.;
Buchwald, S. L. Org. Lett. 1999, 1, 35. (g) Watanabe, M.;
Yamamoto, T.; Nishiyama, M. Angew. Chem. Int. Ed. 2000,
39, 2501. (h) Brown, J. A. Tetrahedron Lett. 2000, 41,
1623. (i) Song, J. J.; Yee, N. K. Org. Lett. 2000, 2, 519.
(j) Song, J. J.; Yee, N. K. Tetrahedron Lett. 2001, 42, 2937.
(k) Yu, Y.; Ostrech, J. M.; Houghten, R. A. Tetrahedron
Lett. 2003, 44, 2569. (l) Qadir, M.; Priestley, R. E.; Rising,
T. W. D.; Gelbrich, T.; Coles, S. M.; Hursthouse, M. B.;
Sheldrake, P. W.; Whittall, N.; Hii, K. K. Tetrahedron Lett.
2003, 44, 3675. (m) Brain, C. T.; Steer, J. T. J. Org. Chem.
2003, 68, 6814.
EI–MS: m/z = 225 [M].
Anal. Calcd for C15H15NO: C, 79.97; H, 6.71; N, 6.22; O, 7.10.
Found: C, 79.77; H, 6.95; N, 6.10.
4-[3,4-Dihydro-1,5-benzoxazepin-5(2H)-yl]benzonitrile (5r)
Yield: 57%; white solid; mp 114–116 °C.
IR (KBr): 2955, 2211, 1606, 1590, 1510, 1490, 1380, 1249, 1175,
1050, 826, 771 cm–1.
1H NMR (200 MHz, CDCl3): d = 7.43 (d, J = 9.0 Hz, 2 H), 7.21–
7.13 (m, 2 H), 7.10 (dd, J = 7.4, 1.6 Hz, 1 H), 7.04 (ddd, J = 7.4, 7.4,
1.6 Hz, 1 H), 6.79 (d, J = 9.0 Hz, 2 H), 4.08 (t, J = 5.2 Hz, 2 H), 3.90
(t, J = 5.6 Hz, 2 H), 2.16–2.04 (m, 2 H).
13C NMR (50 MHz, CDCl3): d = 155.9, 151.3, 135.6, 134.0, 129.1,
128.1, 123.7, 122.9, 120.5, 114.0, 100.0, 70.2, 47.8, 27.5.
EI–MS: m/z = 249 [M+].
Anal. Calcd for C16H14N2O: C, 76.78; H, 5.64; N, 11.19; O, 6.39.
Found: C, 76.65; H, 5.51; N, 11.38.
5-(3-Methoxyphenyl)-2,3,4,5-tetrahydro-1,5-benzoxazepine
(5s)
Yield: 55%; yellow oil.
IR (KBr): 2960, 2867, 1612, 1578, 1594, 1492, 1465, 1248, 1165,
1042, 757 cm–1.
1H NMR (400 MHz, CDCl3): d = 7.17–6.98 (m, 4 H), 6.93 (ddd,
J = 7.6, 7.6, 2.0 Hz, 1 H), 6.49 (dd, J = 8.4, 2.4 Hz, 1 H), 6.43 (dd,
J = 2.4, 2.0 Hz, 1 H), 6.34 (dd, J = 8.4, 2.4 Hz, 1 H), 4.09 (t, J = 5.6
Hz, 2 H), 3.88 (t, J = 6.4 Hz, 2 H), 3.72 (s, 3 H), 2.13–2.02 (m, 2 H).
(5) (a) Hartwig, J. F.; Kawatsura, M.; Hauck, S. I.;
Shaughnessy, K. H.; Alcazar-Roman, L. M. J. Org. Chem.
1999, 64, 5575. (b) Old, D. W.; Harris, M. C.; Buchwald, S.
L. Org. Lett. 2000, 2, 1403. (c) Meneyrol, J.; Helissey, P.;
Tratrat, C.; Giorgi-Renault, S.; Husson, H.-P. Synth.
Commun. 2001, 31, 987.
(6) (a) Beller, M.; Breindl, C.; Riermeier, T. H.; Eichberger, M.;
Trauthwein, H. Angew. Chem. Int. Ed. 1998, 37, 3389.
(b) Beller, M.; Breindl, C.; Riermeier, T. H.; Tillack, A. J.
Org. Chem. 2001, 66, 1403.
13C NMR (100 MHz, CDCl3): d = 161.1, 155.8, 149.8, 130.4, 129.1,
126.2, 122.9, 122.0, 108.5, 103.6, 102.2, 69.9, 55.5, 47.7, 27.6.
EI–MS: m/z = 255 [M].
Anal. Calcd for C16H17NO2: C, 75.27; H, 6.71; N, 5.49; O, 12.53.
Found: C, 75.01; H, 6.63; N, 5.52.
(7) (a) Herrmann, W. A.; Reisinger, C. P.; Spiegler, M. J.
Organomet. Chem. 1998, 557, 93. (b) Böhm, V. P. W.;
Gstöttmayr, C. W. K.; Weskamp, T.; Herrmann, W. A. J.
Organomet. Chem. 2000, 595, 186. (c) Bourissou, D.;
Guerret, O.; Gabbaï, F. P.; Bertrand, G. Chem. Rev. 2000,
100, 39. (d) Herrmann, W. A. Angew. Chem. Int. Ed. 2002,
41, 1290.
(8) (a) Gradel, B.; Brenner, E.; Schneider, R.; Fort, Y.
Tetrahedron Lett. 2001, 42, 5689. (b) Desmarets, C.;
Schneider, R.; Fort, Y. J. Org. Chem. 2002, 67, 3029.
(9) Omar-Amrani, R.; Thomas, A.; Brenner, E.; Schneider, R.;
Fort, Y. Org. Lett. 2003, 5, 2311.
References
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Synthesis 2004, No. 15, 2527–2534 © Thieme Stuttgart · New York