Organic Letters
Letter
Scheme 1. Synthesis of A3B-Type Tetraamide Porphyrin 4
(3) See examples from benzenetricarboxamides: (a) Viault, G.;
Dautrey, S.; Maindron, N.; Hardouin, J.; Renard, P.-Y.; Romieu, A.
Org. Biomol. Chem. 2013, 11, 2693. Cyclohexane trisamides: (b) van
Bommel, K. J. C.; Stuart, M. C. A.; Feringa, B. L.; van Esch, J. Org.
Biomol. Chem . 2005, 3, 2917. Phloroglucinol triamides: (c) Baker, M.
B.; Ghiviriga, I.; Castellano, R. K. Chem. Sci. 2012, 3, 1095. Bipyridine
discotics: (d) Petkau-Milroy, K.; Sonntag, M. H.; Colditz, A.;
In summary, A3B-type monocarboxyphenyl porphyrins can
be readily generated from TCPP or from its tetramethyl ester
derivative 2. We have demonstrated the feasibility of a direct
synthetic pathway with no protecting groups to monoacid
triamide porphyrin 1. When a diverse pair of substituents must
be attached to the meso-carboxyphenyl porphyrin core,
however, we recommend using intermediate 3, which can be
expediently prepared in very good yields.24 The operational
simplicity of its synthesis and the ease of purification should
make it particularly appealing in areas of chemical research
where porphyrins with a single addressable attachment point
are desired.25 Further reports on utilizing such molecules in the
construction of supramolecular materials will be presented in
due time.
Brunsveld, L. Int. J. Mol. Sci. 2013, 14, 21189.
Calixarenes:
(e) Fischer, C.; Lin, G.; Seichter, W.; Weber, E. Tetrahedron 2011, 67,
5656. Cyclodextrins: (f) Nelson, A.; Stoddart, J. F. Org. Lett. 2003, 5,
3783. Phthalocyanines: (g) Cid, J.-J.; Garcia-Iglesias, M.; Yum, J.-H.;
Forneli, A.; Albero, J.; Martinez-Ferrero, E.; Vazquez, P.; Gratzel, M.;
̈
Nazeeruddin, M. K.; Palomares, E.; Torres, T. Chem.Eur. J. 2009,
15, 5130.
(4) For reviews, see: (a) Sengupta, S.; Wurthner, F. Acc. Chem. Res.
̈
2013, 46, 2498. (b) Beletskaya, I.; Tyurin, V. S.; Tsivadze, A. Y.;
Guilard, R.; Stern, C. Chem. Rev. 2009, 109, 1659.
ASSOCIATED CONTENT
* Supporting Information
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(5) Cao, X.; Lin, W.; Yu, Q. J. Org. Chem. 2011, 76, 7423.
(6) Ellis, A.; Gooch, D.; Twyman, L. J. J. Org. Chem. 2013, 78, 5364.
(7) Rhee, J.-K.; Baksh, M.; Nycholat, C.; Paulson, J. C.; Kitagishi, H.;
Finn, M. G. Biomacromol 2012, 13, 2333.
(8) (a) Zhang, H.; Liu, Q.; Li, J.; Qu, D.-H. Org. Lett. 2013, 15, 338.
(b) Marois, J.-S.; Cantin, K.; Desmarais, A.; Morin, J.-F. Org. Lett.
2008, 10, 33.
(9) (a) Ambre, R. B.; Chang, G.-F.; Hung, C.-H. Chem. Commun.
2014, 50, 725. (b) Mojiri-Foroushani, M.; Dehghani, H.; Salehi-
Vanani, N. Electrochim. Acta 2013, 92, 315.
S
Reaction schemes, detailed experimental procedures, UV−vis,
IR, NMR, and MALDI spectra. This material is available free of
AUTHOR INFORMATION
Corresponding Author
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Notes
(10) (a) Helmich, F.; Lee, C. C.; Nieuwenhuizen, M. M. L.; Gielen, J.
C.; Christianen, P. C. M.; Larsen, A.; Fytas, G.; Leclere, P. E. L. G.;
Schenning, A. P. H. J.; Meijer, E. W. Angew. Chem., Int. Ed. 2010, 49,
3939. (b) Hoeben, F. J. M.; Wolffs, M.; Zhang, J.; De Feyter, S.;
Leclere, P.; Schenning, A. P. H. J.; Meijer, E. W. J. Am. Chem. Soc.
2007, 129, 9819.
(11) Shi, X.; Barkigia, K. M.; Fajer, J.; Drain, C. M. J. Org. Chem.
2001, 66, 6513.
(12) Lindsey, J. S. Acc. Chem. Res. 2010, 43, 300.
(13) Senge, M. O. Chem. Commun. 2011, 47, 1943.
(14) (a) Sforazzini, G.; Turdean, R.; Sakai, N.; Matile, S. Chem. Sci.
2013, 4, 1847. (b) Ohtani, M.; Saito, K.; Fukuzumi, S. Chem.Eur. J.
2009, 15, 9160.
(15) Wallace, J. U.; Chen, S. H. Ind. Eng. Chem. Res. 2006, 45, 4494.
(16) 2 is in fact the synthetic precursor of TCPP.
(17) Adler, A. D.; Longo, F. R.; Finarelli, J. D.; Goldmacher, J.;
Assour, J.; Korsakoff, L. J. Org. Chem. 1967, 32, 476.
(18) Nicolaou, K. C.; Estrada, A. A.; Zak, M.; Lee, S. H.; Safina, B. S.
Angew. Chem., Int. Ed. 2005, 44, 1378.
(19) Motorina, I. A.; Huel, C.; Quiniou, E.; Mispelter, J.; Adjadj, E.;
Grierson, D. S. J. Am. Chem. Soc. 2001, 123, 8.
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
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The authors would like to thank Drs. Anja Palmans, Elisa
Huerta, Matthew Baker, and Miguel Garcia from the Institute
for Complex Molecular Systems and Laboratory of Macro-
molecular and Organic Chemistry, Eindhoven University of
Technology for helpful suggestions and discussions. Funding
from the Ministry of Education, Culture and Science (Gravity
Program 024.001.035), The Netherlands Organization for
Scientific Research (NWO), the European Research Council
(FP7/2007−2013) ERC Grant Agreement 246829, and the
Dutch National Research School Combination Catalysis
Controlled by Chemical Design (NRSC-C) is greatly
appreciated.
REFERENCES
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(1) Aida, T.; Meijer, E. W.; Stupp, S. I. Science 2012, 335, 813.
(2) (a) de Torres, M.; van Hameren, R.; Nolte, R. J. M.; Rowan, A.
E.; Elemans, J. A. A. W. Chem. Commun. 2013, 49, 10787. (b) Zhang,
Y.; Chen, P.; Liu, M. Chem.Eur. J. 2008, 14, 1793. (c) Heeres, A.;
van der Pol, C.; Stuart, M.; Friggeri, A.; Feringa, B. L.; van Esch, J. J.
Am. Chem. Soc. 2003, 125, 14252.
(20) Furlan, R. L. E.; Mata, E. G.; Mascaretti, O. A. Tetrahedron
1998, 13023.
(21) See Supporting Information for details.
(22) While we did not detect capping of the anilines as reported
elsewhere,23 the major impurity of the first coupling reaction was
1866
dx.doi.org/10.1021/ol500182z | Org. Lett. 2014, 16, 1864−1867