4744
A. T. P. C. Gomes et al. / Tetrahedron Letters 52 (2011) 4741–4744
Alonso, C. M. A.; Serra, V. I. V.; Neves, M. G. P. M. S.; Tomé, A. C.; Silva, A. M. S.;
Paz, F. A. A.; Cavaleiro, J. A. S. Org. Lett. 2007, 9, 2305–2308; (c) Cunha, A. C.;
Gomes, A. T. P. C.; Ferreira, V. F.; Souza, M. C. B. V.; Neves, M. G. P. M. S.; Tomé,
A. C.; Silva, A. M. S.; Cavaleiro, J. A. S. Synthesis 2010, 510–514; (d) Carvalho, C.
M. B.; Neves, M. G. P. M. S.; Tomé, A. C.; Paz, F. A. A.; Silva, A. M. S.; Cavaleiro, J.
A. S. Org. Lett. 2011, 13, 130–133.
program for funding this work. Ana T.P.C. Gomes thanks FCT for her
PhD Grant (SFRH/BD/38528/2007). Thanks are also due to FCT for
specific funding towards the purchase of the single-crystal diffrac-
tometer and the Portuguese National NMR Network.
18. Reaction of porphyrin 1 with EDA: To a dry dichloromethane (6 mL) solution of
Supplementary data
porphyrin 1 (50 mg, 72.0
40 °C, under a nitrogen atmosphere, was added dropwise a solution of EDA
(75.7 L, 0.72 mmol, 10 equiv) in dichloromethane (5 mL) during 10 h using a
lmol) and Rh2(OAc)4 (3.2 mg, 7.2 lmol, 0.1 equiv), at
l
Supplementary data (crystal structure of compound 3 in CIF
format and the corresponding check CIF report are presented) asso-
ciated with this article can be found, in the online version, at
syringe pump. The reaction mixture was further stirred at the same
temperature for 8 h. The solvent was then evaporated under reduced
pressure and the residue was fractionated by column chromatography (silica
gel) using CH2Cl2 as the eluent. The obtained fractions were further purified by
preparative TLC using a mixture of hexane and ethyl acetate (4:1) as the eluent.
19. Compound 2: 1H NMR (300 MHz, CDCl3): d 9.06 and 8.97 (AB, J = 4.7 Hz, 4H, H-
2,3 and H-7,8), 8.93 (br s, 4H, H-12,13 and H-17,18), 8.23–8.21 (m, 6H, Ho-Ph-
10,15,20), 8.07 (d, J = 8.6 Hz, 2H, Ho-Ph-5), 7.77–7.71 (m, 9H, Hm,p-Ph-10,15,
20), 6.97 (d, J = 8.6 Hz, 2H, Hm-Ph-5), 4.38 (s, 4H, CH2-10), 4.33 (quart,
J = 7.1 Hz, 4H, OCH2CH3), 1.37 (t, J = 7.1 Hz, 6H, OCH2CH3). 13C NMR (75 MHz,
CDCl3): d 171.1 (C@O), 150.7, 150.1, 150.0, 147.3 (Cp-Ph-5), 142.9, 135.4 (Co-
Ph-5), 134.4 (Co-Ph-10,15,20), 132.7, 132.2 and 131.88 and 131.86 and 131.7
(b-C), 127.4 and 126.5 (Cm,p-Ph-10,15,20), 121.5, 120.9, 120.7, 110.7 (Cm-Ph-
References and notes
1. Faustino, M. A. F.; Tomé, A. C.; Neves, M. G. P. M. S.; Silva, A. M. S.; Cavaleiro, J.
A. S. Arkivoc 2005, ix, 332–343.
2. Nyman, E. S.; Hynninen, P. H. J. Photochem. Photobiol. B 2004, 73, 1–28.
3. Chavan, S. A.; Maes, W.; Gevers, L. E. M.; Wahlen, J.; Vankelecom, I. F. J.; Jacobs,
P. A.; Dehaen, W.; De Vos, D. E. Chem. Eur. J. 2005, 11, 6754–6762.
4. (a) Kim, D.; Heo, J.; Ham, S.; Yoo, H.; Lee, C.; Yoon, H.; Ryu, D.; Kim, D.; Jang, W.
Chem. Commun. 2011, 47, 2405–2407; (b) Serra, V. V.; Andrade, S. M.; Neves, M.
G. P. M. S.; Cavaleiro, J. A. S.; Costa, S. M. B. New J. Chem. 2010, 34, 2757–2765.
5. Ferreira, V. F. Curr. Org. Chem. 2007, 11, 177–193.
6. Davies, H. M. L.; Dick, A. R. Top. Curr. Chem. 2010, 292, 303–345.
7. Zollinger, H. In Diazo-Chemistry II—Aliphatic In Inorganic and Organometallic
Compounds; VCH Publichers: New York, 1995.
8. Ferreira, V. F.; Souza, M. C. B. V.; Cunha, A. C.; da Silva, F. C.; Rianelli, R. S.;
Ferreira, S. B. In Modern Approaches to the Synthesis of O - and N -Heterocycles;
Kaufman, T. S., Larghi, E. L., Eds.; Research Signpost: Kerala, 2007; Vol. 3, pp
1–44.
9. (a) Liu, B.; Zhu, S. F.; Zhang, W.; Chen, C.; Zhou, Q. L. J. Am. Chem. Soc. 2007, 129,
5834–5835; (b) Zhang, X.; Ma, M.; Wang, J. Arkivoc 2003, ii, 84–91.
10. Slattery, C. N.; Ford, A.; Maguire, A. R. Tetrahedron 2010, 66, 6681–6705.
11. Some reviews: (a) Doyle, M. P. Chem. Rev. 1980, 86, 919–940; (b) Ye, T.;
Mckervey, M. A. Chem. Rev. 1994, 94, 1091–1160; (c) Davies, H. M. L.; Beckwith,
R. E. Chem. Rev. 2003, 103, 2861–2903.
5), 61.3 (CH2-10), 53.7 (OCH2CH3), 14.3 (OCH2CH3). UV–vis (CHCl3): kmax (log
e)
420 (5.14), 505 (3.39), 548 (3.86), 587 (3.35) nm. HRMS-ESI: m/z 863.2445.
Calcd. for C52H41N5O4Zn (M+) 863.2450.
Compound 3: 1H NMR (300 MHz, CDCl3): d 9.13 (s, 1H, NH), 9.95–8.93 (m, 8H,
H-2,3,7,8,12,13,17,18), 8.24–8.21 (m, 6H, Ho-Ph-10,15,20), 8.13 (d, J = 8.4 Hz,
2H, Ho-Ph-5), 7.77–7.72 (m, 9H, Hm,p-Ph-10,15,20), 7.69 (d, J = 8.4 Hz, 2H, Hm-
Ph-5), 4.30 (quart, J = 7.1 Hz, 2H, OCH2CH3), 4.16 (s, 2H, CH2-20), 3.79 (s, 2H,
CH2-10), 1.34 (t, J = 7.1 Hz, 3H, OCH2CH3). 13C NMR (75 MHz, CDCl3): d 170.3
(CO2Et), 167.1 (CONH), 150.2, 150.1, 142.8, 138.9, 136.5, 134.8 (Co-Ph-5), 134.4
(Co-Ph-10,15,20), 132.0 (b-C), 131.9 (b-C), 127.4 and 126.5 (Cm,p-Ph-10,15,20),
121.1, 121.0, 120.4, 117.8, 117.7 (Cm-Ph-5), 71.7 (CH2-10), 69.3 (CH2-20), 61.6
(OCH2), 14.2 (OCH2CH3). UV–vis (CHCl3): kmax (log e) 423 (5.59), 517 (3.47),
552 (4.26), 595 (3.72) nm. HRMS-ESI: m/z 835.2131. Calcd. for C50H37N5O4Zn
(M+) 835.2137.
Compound 4: 1H NMR (300 MHz, CDCl3): d 9.35 (s, 1H, NH), 8.89–8.87 (m, 8H,
H-2,3,7,8,12,13,17,18), 8.24–8.19 (m, 6H, Ho-Ph-10,15,20), 7.97 (d, J = 7.9 Hz,
2H, Ho-Ph-5), 7.79–7.70 (m, 11H, Hm,p-Ph-5,10,15,20), 4.30 (s, 2H, CH2-10). 13C
NMR (126 MHz, CDCl3): d 167.7 (C@O), 150.3, 150.3, 150.2, 150.1, 142.8, 135.0,
134.4, 131.9, 131.9, 127.4, 127.4, 127.4, 126.5, 121.1, 121.1, 29.7 (CH2-10). UV–
12. Callot, H. J. Tetrahedron Lett. 1972, 13, 1011–1014.
13. Gomes, A. T. P. C.; Leão, R. A. C.; Alonso, C. M. A.; Neves, M. G. P. M. S.; Faustino,
M. A. F.; Tomé, A. C.; Silva, A. M. S.; Pinheiro, S.; Souza, M. C. B. V.; Ferreira, V. F.;
Cavaleiro, J. A. S. Helv. Chim. Acta 2008, 91, 2270–2283.
14. Tomé, A. C.; Lacerda, P. S. S.; Neves, M. G. P. M. S.; Cavaleiro, J. A. S. Chem.
Commun. 1997, 1199–1200.
vis (CHCl3): kmax (log e) 418 (5.71), 510 (3.46), 546 (3.82), 584 (3.35) nm.
HRMS-ESI: m/z 749.1764. Calcd. for C46H31N5O2Zn (M+) 749.1769.
20. Candeias, N. R.; Gois, P. M. P.; Afonso, C. A. M. J. Org. Chem. 2006, 71, 5489–
5497.
21. Senge, M. O.; Smith, K. M. J. Chem. Soc., Chem. Commun. 1994, 923–924.
22. (a) Allen, F. H. Acta Cryst. B 2002, 58, 380–388; (b) Allen, F. H.; Motherwell, W.
D. S. Acta Cryst. B 2002, 58, 407–422.
23. Tsuda, A. Bull. Chem. Soc. Japan 2009, 82, 11–28.
24. Shultz, A. M.; Farha, O. K.; Hupp, J. T.; Nguyen, S. T. J. Am. Chem. Soc. 2009, 131,
4204–4205.
25. Collman, J. P.; McDevitt, J. T.; Yee, G. T.; Leidner, C. R.; McCullough, L. G.; Little,
W. A.; Torrance, J. B. P. Natl. Acad. Sci. 1986, 83, 4581–4585.
26. Davidson, G. J. E.; Lane, L. A.; Raithby, P. R.; Warren, J. E.; Robinson, C. V.;
Sanders, J. K. M. Inorg. Chem. 2008, 47, 8721–8726.
27. (a) Diskin-Posner, Y.; Patra, G. K.; Goldberg, I. Eur. J. Inorg. Chem. 2001, 2515–
2523; (b) George, S.; Lipstman, S.; Muniappan, S.; Goldberg, I. Cryst. Eng.
Commun. 2006, 8, 417–424; (c) Runge, S.; Senge, M. O. Z. Naturforsch., B 1998,
53, 1021–1030.
15. (a) Silva, A. M. G.; Tomé, A. C.; Neves, M. G. P. M. S.; Silva, A. M. S.; Cavaleiro, J.
A. S. Chem. Commum. 1999, 1767–1768; (b) Silva, A. M. G.; Tomé, A. C.; Neves,
M. G. P. M. S.; Silva, A. M. S.; Cavaleiro, J. A. S. J. Org. Chem. 2005, 70, 2306–2314;
(c) Silva, A. M. G.; Lacerda, P. S. S.; Tomé, A. C.; Neves, M. G. P. M. S.; Silva, A. M.
S.; Cavaleiro, J. A. S.; Makarova, E. A.; Lukyanets, E. A. J. Org. Chem. 2006, 71,
8352–8356; (d) Lacerda, P. S. S.; Silva, A. M. G.; Tomé, A. C.; Neves, M. G. P. M.
S.; Silva, A. M. S.; Cavaleiro, J. A. S.; Llamas-Saiz, A. L. Angew. Chem., Int. Ed.
2006, 45, 5487–5491.
16. (a) Silva, A. M. G.; Oliveira, K. T.; Faustino, M. A. F.; Neves, M. G. P. M. S.; Tomé,
A. C.; Silva, A. M. S.; Cavaleiro, J. A. S.; Brandão, P.; Felix, V. Eur. J. Org. Chem.
2008, 704–712; (b) Pereira, A. M. V. M.; Alonso, C. M. A.; Neves, M. G. P. M. S.;
Tomé, A. C.; Silva, A. M. S.; Paz, F. A. A.; Cavaleiro, J. A. S. J. Org. Chem. 2008, 73,
7353–7356.
17. (a) Soares, A. R. M.; Martínez-Díaz, M. V.; Bruckner, A.; Pereira, A. M. V. M.;
Tomé, J. P. C.; Faustino, M. A. F.; Neves, M. G. P. M. S.; Tomé, A. C.; Silva, A. M. S.;
Cavaleiro, J. A. S.; Torres, T.; Guldi, D. M. Org. Lett 2007, 9, 1557–1560; (b)
28. Senge, M. O.; Speck, M.; Wiehe, A.; Dieks, H.; Aguirre, S.; Kurreck, H. Photochem.
Photobiol. 1999, 70, 206–216.