9942
R.N. Davis, T.D. Lash / Tetrahedron 65 (2009) 9935–9943
3. Vogel, E.; Haas, W.; Knipp, B.; Lex, J.; Schmickler, H. Angew. Chem., Int. Ed. Engl.
d6-DMSO):
d 7.20–7.34 (2H, m), 7.35–7.55 (3H, m), 7.55–7.62 (3H,
1988, 27, 406–409.
4. Lash, T. D. Synlett 2000, 279–295.
5. Cyranski, M. K.; Krygowski, T. M.; Wisiorowski, M.; Hommes, N. J. R.; van, E.;
Schleyer, P.; von, R. Angew. Chem., Int. Ed. 1998, 37, 177–180.
6. Aihara, J.-i. J. Phys. Chem. A 2008, 112, 5305–5311.
m), 7.78 (1H, d, J¼7.8 Hz), 7.84 (2H, d, J¼7.5 Hz), 7.90 (1H, s), 7.96
(1H, d, J¼7.2 Hz), 8.05 (1H, s), 8.62 (1H, d, J¼7.2 Hz), 13.01 (1H, br s);
13C NMR (75 MHz, d6-DMSO):
d 110.8,119.1,119.3,121.5,122.7, 123.1,
124.4, 125.6, 127.2, 128.76, 128.85, 130.2, 131.0, 134.0, 134.8, 136.2,
137.83, 137.88, 138.6, 144.0, 147.8; EIMS (70 eV): m/z (rel int.) 322
(8.6), 321 (25), 320 (100, Mþ), 319 (57), 292 (3.1), 277 (3.8), 232
(31); HRMS (EI), m/z calcd for C23H16N2: 320.1314. Found: 320.1310.
Anal. calcd for C40H26N4$1/2CHCl3: C, 74.26; H, 4.38; N, 7.37. Found:
C, 74.22; H, 4.45; N, 7.19.
7. Berlin, K. Angew. Chem., Int. Ed. 1996, 35, 1820–1822.
8. Lash, T. D.; Hayes, M. J. Angew. Chem., Int. Ed. 1997, 36, 840–842.
9. (a) Lash, T. D.; Hayes, M. J.; Spence, J. D.; Muckey, M. A.; Ferrence, G. M.;
Szczepura, L. F. J. Org. Chem. 2002, 67, 4860–4874; (b) Liu, D.; Lash, T. D. J. Org.
Chem. 2003, 68, 1755–1761.
10. Muckey, M. A.; Szczepura, L. F.; Ferrence, G. M.; Lash, T. D. Inorg. Chem. 2002, 41,
4840–4842.
11. Lash, T. D.; Colby, D. A.; Szczepura, L. F. Inorg. Chem. 2004, 43, 5258–5267.
12. Lash, T. D.; Rasmussen, J. M.; Bergman, K. M.; Colby, D. A. Org. Lett. 2004, 6,
549–552.
13. Hayes, M. J.; Spence, J. D.; Lash, T. D. Chem. Commun. 1998, 2409–2410.
14. Lash, T. D.; Muckey, M. A.; Hayes, M. J.; Liu, D.; Spence, J. D.; Ferrence, G. M.
J. Org. Chem. 2003, 68, 8558–8570.
15. Morganthaler, J. B.; Peters, S. J.; Ceden˜o, D. L.; Constantino, M. H.; Edwards, K.
A.; Kamowski, E. M.; Passini, J. C.; Butkus, B. E.; Young, A. M.; Lash, T. D.; Jones,
M. A. Bioorg. Med. Chem. 2008, 16, 7033–7038.
16. Lash, T. D. In The Porphyrin Handbook; Kadish, K. M., Smith, K. M., Guilard, R.,
Eds.; Academic: San Diego, 2000; Vol. 2, pp 125–199.
4.2.15. 12-(2,4-Dimethoxyphenylmethylene)benzo[b]indeno[1,2-f]-
1,4-diazepine (29d). Fulvene 21d (202 mg, 0.69 mmol), cerium tri-
chloride heptahydrate (281 mg), and o-phenylenediamine (79 mg,
0.73 mmol) were reacted under the previous conditions. The product
was purified by column chromatography on grade three basic alu-
mina, eluting with 60% dichloromethane–hexanes, and recrystal-
lized from chloroform–hexanes to give the diazepine (150 mg,
0.39 mmol, 57%) as a yellow solid, mp 246–247 ꢁC; 1H NMR
17. Lash, T. D. Eur. J. Org. Chem. 2007, 5461–5481.
18. (a) Lash, T. D.; Chaney, S. T. Tetrahedron Lett. 1996, 37, 8825–8828; (b) Bergman,
K. M.; Ferrence, G. M.; Lash, T. D. J. Org. Chem. 2004, 69, 7888–7897.
19. Lash, T. D. Angew. Chem., Int. Ed. Engl. 1995, 34, 2533–2535.
20. Lash, T. D.; Chaney, S. T.; Richter, D. T. J. Org. Chem. 1998, 63, 9076–9088.
21. Richter, D. T.; Lash, T. D. Tetrahedron 2001, 57, 3659–3673.
22. El-Beck, J. A.; Lash, T. D. Org. Lett. 2006, 8, 5263–5266.
23. Hayes, M. J.; Lash, T. D. Chem.d Eur. J. 1998, 4, 508–511.
24. Lash, T. D.; Chaney, S. T. Angew. Chem., Int. Ed. 1997, 36, 839–840.
25. (a) Lash, T. D.; Colby, D. A.; Graham, S. R.; Chaney, S. T. J. Org. Chem. 2004, 69,
8851–8864; (b) Lash, T. D.; El-Beck, J. A.; Ferrence, G. M. J. Org. Chem. 2007, 72,
8402–8415.
(400 MHz, d6-DMSO):
d 3.89 (3H, s), 3.93 (3H, s), 6.74 (1H, s), 6.76
(1H, d, J¼8.4 Hz), 7.20–7.30 (2H, m), 7.30–7.42 (2H, m), 7.55 (1H, d,
J¼8 Hz), 7.76–7.82 (2H, m), 7.88 (1H, d, J¼7.6 Hz), 7.92 (1H, s), 7.93
(1H, s), 8.60 (1H, d, J¼7.6 Hz), 12.93 (1H, s); 13C NMR (75 MHz, d6-
DMSO): d 55.3, 55.7, 98.3, 106.2, 110.7, 117.8, 118.8, 119.0, 121.3, 122.5,
122.9, 124.9, 125.3, 126.0, 126.6, 132.1, 133.3, 134.0, 135.6, 137.7, 138.4,
144.0, 148.1, 159.5, 162.0; EIMS (70 eV): m/z (rel int.) 382 (7.9), 381
(28), 380 (100, Mþ), 379 (10), 365 (12); HRMS (EI), m/z calcd for
C25H20N2O2: 380.1525. Found: 380.1520. Anal. calcd for C25H20N2O2:
C, 78.93; H, 5.30; N, 7.36. Found: C, 78.43; H, 5.30; N, 7.15.
26. (a) Lash, T. D. Chem. Commun. 1998, 1683–1684; (b) Colby, D. A.; Ferrence, G. M.;
Lash, T. D. Angew. Chem., Int. Ed. 2004, 43, 1346–1349.
27. (a) Colby, D. A.; Lash, T. D. Chem.dEur. J. 2002, 8, 5397–5402; (b) Lash, T. D.;
Colby, D. A.; Ferrence, G. M. Eur. J. Org. Chem. 2003, 4533–4548; (c) El-Beck, J. A.;
Lash, T. D. Eur. J. Org. Chem. 2007, 3981–3990.
4.2.16. 12-(5-Bromo-2,4-dimethoxyphenylmethylene)benzo[b]indeno[1,2-
f]-1,4-diazepine (29e). Fulvene 35d (51 mg, 0.14 mmol), cerium tri-
chloride heptahydrate (53 mg), and o-phenylenediamine (18 mg,
0.17 mmol) were reacted under the previous conditions. The product
was purified by column chromatography on grade three basic alumina,
eluting with 60% dichloromethane–hexanes, and recrystallized from
chloroform–hexanes to give the diazepine (43 mg, 0.094 mmol, 67%) as
28. (a) Stepien, M.; Latos-Grazynski, L. Chem.dEur. J. 2001, 7, 5113–5117; (b) Ste-
pien, M.; Latos-Grazynski, L. Acc. Chem. Res. 2005, 38, 88–98.
29. (a) Szymanski, J. T.; Lash, T. D. Tetrahedron Lett. 2003, 44, 8613–8616; (b) Lash,
T. D.; Szymanski, J. T.; Ferrence, G. M. J. Org. Chem. 2007, 72, 6481–6492.
30. (a) Graham, S. R.; Ferrence, G. M.; Lash, T. D. Chem. Commun. 2002, 894–895; (b)
Lash, T. D.; Colby, D. A.; Graham, S. R.; Ferrence, G. M.; Szczepura, L. F. Inorg.
Chem. 2003, 42, 7326–7338; (c) Liu, D.; Ferrence, G. M.; Lash, T. D. J. Org. Chem.
2004, 69, 6079–6093.
31. (a) Stepien, M.; Latos-Grazynski, L.; Lash, T. D.; Szterenberg, L. Inorg. Chem.
2001, 40, 6892–6900; (b) Venkatraman, S.; Anand, V. G.; Pushpan, S. K.; Sankar,
J.; Chandrashekar, T. K. Chem. Commun. 2002, 462; (c) Stepien, M.; Latos-Gra-
zynski, L.; Szterenberg, L.; Panek, J.; Latajka, Z. J. Am. Chem. Soc. 2004, 126,
4566–4580.
an orange solid, mp 285–286 ꢁC; 1H NMR (400 MHz, d6-DMSO):
d 4.00
(3H, s), 4.01 (3H, s), 6.91 (1H, s), 7.20–7.30 (2H, m), 7.30–7.42 (2H, m), 7.59
(1H, d, J¼8.0 Hz), 7.77 (1H, d, J¼8.0 Hz), 7.82–7.90 (3H, m), 7.90 (1H, s),
8.63 (1H, d, J¼7.6 Hz), 13.04 (1H, s); 13C NMR (100 MHz, d6-DMSO):
d
56.2, 56.5, 97.5, 101.7, 110.8, 118.7, 118.9, 119.0, 121.4, 122.7, 123.0, 124.1,
32. Lash, T. D. Macroheterocycles 2008, 1, 9–20.
33. Latos-Grazynski, L. In The Porphyrin Handbook; Kadish, K. M., Smith, K. M.,
Guilard, R., Eds.; Academic: San Diego, 2000; Vol. 2, pp 361–416.
34. Srinivasan, A.; Furuta, H. Acc. Chem. Res. 2005, 38, 10–20.
35. Harvey, J. D.; Ziegler, C. J. Coord. Chem. Rev. 2003, 247, 1–19.
36. (a) Liu, B. Y.; Bru¨ckner, C.; Dolphin, D. Chem. Commun. 1996, 2141–2142; (b)
Lash, T. D.; Richter, D. T.; Shiner, C. M. J. Org. Chem. 1999, 64, 7973–7982; (c)
Lash, T. D.; Von Ruden, A. L. J. Org. Chem. 2008, 73, 9417–9425.
37. For related N-confused pyriporphyrins and pyrazole-containing analogues of
the porphyrins, see: (a) Lash, T. D.; Pokharel, K.; Serling, J. M.; Yant, V. R.;
Ferrence, G. M. Org. Lett. 2007, 9, 2863–2866; (b) Lash, T. D.; Young, A. M.; Von
Ruden, A. L.; Ferrence, G. M. Chem. Commun. 2008, 6309–6311.
38. (a) Furuta, H.; Asano, T.; Ogawa, T. J. Am. Chem. Soc. 1994, 116, 767–768; (b)
Chmielewski, P. J.; Latos-Grazynski, L.; Rachlewicz, K.; Glowiak, T. Angew. Chem.,
Int. Ed. Engl. 1994, 33, 779–781.
39. Lash, T. D.; Romanic, J. L.; Hayes, M. J.; Spence, J. D. Chem. Commun. 1999,
819–820.
40. Furuta, H.; Maeda, H.; Osuka, A. J. Am. Chem. Soc. 2000, 122, 803–807.
41. Maeda, H.; Osuka, A.; Furuta, H. J. Am. Chem. Soc. 2003, 125, 15690–15691.
42. Graham, S. R.; Colby, D. A.; Lash, T. D. Angew. Chem., Int. Ed. 2002, 41, 1371–
1374.
124.4,125.5,126.9,133.7,134.0,134.1,136.5,137.6,138.5,143.9,147.9,157.4,
158.9; HRMS (EI), m/z calcd for C25H19BrN2O2: 458.0630. Found:
458.0628. Anal. calcd for C25H19BrN2O2.H2O: C, 62.90; H, 4.43; N, 5.87.
Found: C, 63.11; H, 4.19; N, 5.86.
Acknowledgements
This material is based upon work supported by the National
Science Foundation under Grant No. CHE-0616555 and the Petro-
leum Research Fund, administered by the American Chemical So-
ciety. Funding for a 500 MHz Bruker Avance III NMR spectrometer
was provided by the National Science Foundation under grant no.
CHE-0722385.
Supplementary data
43. The synthesis of resorcinol-derived dicarbaporphyrinoids has also been noted:
Xu, L.; Lash, T. D. Tetrahedron Lett. 2006, 47, 8863–8866.
Supplementary data associated with this article can be found in
44. Miyake, K.; Lash, T. D. Chem. Commun. 2004, 178–179.
45. Lash, T. D.; Colby, D. A.; Idate, A. S.; Davis, R. N. J. Am. Chem. Soc. 2007, 129,
13801–13802.
46. Zhang, Z.; Ferrence, G. M.; Lash, T. D. Org. Lett. 2009, 11, 101–104.
47. Lash, T. D. Chem.dEur. J. 1996, 2, 1197–1200.
48. These results were presented, in part, at the following meetings: (a)
231st National American Chemical Society Meeting, Atlanta, GA, March
2006 (Davis, R.N.; Lash, T.D. Book of Abstracts, ORGN 535); (b) Great
Lakes Regional Meeting of the American Chemical Society, Milwaukee,
References and notes
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