Paper
Organic & Biomolecular Chemistry
7.23 (m, 4H, phenyl), 7.12 (br s, 1H, β-pyrrole), 6,96 (br s, 1H,
β-pyrrole), 4.55 (s, 2H, –CH2-triazole), 2.39 (s, 3H, –CH3-tolyl),
1.49 (s, 9H, –tBu), 1.44 (s, 9H, –tBu), 1.42 (s, 9H, –tBu). MS
(FAB): m/z 970(M+).
Anal. Calcd for C60H57CuN8O: C, 74.32; H, 5.92; N, 11.56%.
Found: C, 74.36; H, 5.89; N, 11.53%.
(d) C. M. Lemon and P. J. Brothers, J. Porphyrins Phthalo-
cyanines, 2011, 15, 809.
3 J. F. B. Barata, C. I. M. Santos, M. Graça, P. M. S. Neves,
M. Amparo, F. Faustino and J. A. S. Cava, Top. Heterocycl.
Chem., 2014, 33, 79–142.
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D. G. Nocera, Porphyrin and Corrole Platforms for Water
Oxidation, Oxygen Reduction, and Peroxide Dismutation,
Handbook of Porphyrin Science, 2012, vol. 21, pp. 1–143. ,
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3-NHC(O)H-TtBuCorrCu (7). The crude product from the
reduction of 3-(NO2)TtBuCorrCu (50 mg, 0.06 mmol) was dis-
solved in toluene (13 mL) and the solution was heated to
reflux. Then, 1 mL of 85% formic acid was added and the reac-
tion was monitored by UV-Vis spectroscopy. The red-shift of
the Soret band was indicative of the effective formylation of
the amino group. After 20 min, the solution was cooled and
evaporated on a rotary evaporator. The crude material was
applied to a silica gel column, using CHCl3 as eluant. 35 mg of
compound 5 were obtained as a brownish powder after crystal-
lization from CHCl3–MeOH (71% yield). Mp >300 °C. UV-vis
(CH2Cl2): λmax, nm (log ε) 421 (4.99), 631 (3.92). 1H NMR
(300 MHz, CDCl3): 8.56 (1H, br s, β-pyrrole), 7.91 (1H, br s,
β-pyrrole), 7.86 (1H, s, –NHCHO), 7.72 (1H, br s, β-pyrrole),
7.63 (4H, m, phenyl), 7.53 (8H, m, phenyl), 7.43 (1H, br s,
β-pyrrole), 7.31 (1H, d, J = 3.99 Hz, β-pyrrole), 7.14 (1H, br s,
β-pyrrole), 7.09 (1H, br s, β-pyrrole), 6.56 (1H, s, –NHCHO),
1.45 (9H, s, –tBu), 1.43 (9H, s, –tBu), 1.42 (9H, s, –tBu). MS
(FAB): m/z 799(M+). Anal. Calcd for C50H49CuN5O: C, 75.11;
H, 6.18; N, 8.76%. Found: C, 75.21; H, 6.13; N, 8.69%.
6 S. Hiroto, I. Hisaki, H. Shinokubo and A. Osuka, Angew.
Chem., Int. Ed., 2005, 44, 6763.
Conclusions
7 (a) A. Mahammed, I. Goldberg and Z. Gross, Org. Lett.,
2001, 3, 3443; (b) A. Mahammed and Z. Gross, J. Porphyrins
Phthalocyanines, 2010, 14, 911.
8 (a) R. Paolesse, S. Nardis, M. Venanzi, M. Mastroianni,
M. Russo, F. R. Fronczek and M. G. H. Vicente, Chem. –
Eur. J., 2003, 9, 1192; (b) I. Saltsman, A. Mahammed,
I. Goldberg, E. Tkachenko, M. Botoshansky and Z. Gross,
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9 C. I. M. Santos, E. Oliveira, J. F. B. Barata, M. A. F. Faustino,
J. A. S. Cavaleiro, S. M. G. P. M. Neves and C. Lodeiro,
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10 K. Sudhakar, V. Velkannan and L. Giribabu, Tetrahedron
Lett., 2012, 53, 991.
Herein we report the first examples of organic manipulation of
the nitro group in a β-functionalized copper corrolate. The
reduction performed on the Cu 3-NO2-5,10,15-triarylcorrolato
offers the corresponding amino-derivative which was exploited
for the further derivatization of corrole macrocycle, via amide
functions. This synthetic tool was demonstrated to be success-
ful, affording easily a number of β-acylated products in good
yields. Notably, it is to highlight that the achievement of
corrole (5) bearing the azidomethyl group has been crucial for
further corrole functionalization by Huisgen “click” reaction.
11 N. Ono, The Nitro Group in Organic Synthesis, Wiley-VHC,
2001.
Acknowledgements
12 (a) M. Stefanelli, M. Mastroianni, S. Nardis, S. Licoccia,
F. R. Fronczek, K. M. Smith, W. Zhu, Z. Ou, K. M. Kadish
and R. Paolesse, Inorg. Chem., 2007, 46, 10791;
(b) M. Mastroianni, W. Zhu, M. Stefanelli, S. Nardis,
F. R. Fronczek, K. M. Smith, Z. Ou, K. M. Kadish and
R. Paolesse, Inorg. Chem., 2008, 47, 11680; (c) M. Stefanelli,
F. Mandoj, M. Mastroianni, S. Nardis, P. Mohite,
F. R. Fronczek, K. M. Smith, K. M. Kadish, X. Xiao, Z. Ou,
P. Chen and R. Paolesse, Inorg. Chem., 2011, 50, 8281;
(d) M. Stefanelli, S. Nardis, L. Tortora, F. R. Fronczek,
K. M. Smith, S. Licoccia and R. Paolesse, Chem. Commun.,
2011, 47, 4255; (e) G. Pomarico, F. R. Fronczek, S. Nardis,
K. M. Smith and R. Paolesse, J. Porphyrins Phthalocyanines,
The support of the Italian MiUR (FIRB project no.
RBFR12WB3W) and the US National Institutes of Health
(grant CA132861) is gratefully acknowledged.
Notes and references
1 R. Paolesse, in The Porphyrin Handbook, ed. K. M. Kadish,
K. M. Smith and R. Guilard, Academic Press, New York,
2000, vol. 2, pp. 201–232.
2 (a) S. Nardis, D. Monti and R. Paolesse, Mini-Rev. Org.
Chem., 2005, 2, 355; (b) R. Paolesse, Synlett, 2008, 2215;
(c) D. T. Gryko, J. Porphyrins Phthalocyanines, 2008, 12, 906;
6206 | Org. Biomol. Chem., 2014, 12, 6200–6207
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