Conjugated macrocycles related to the porphyrins. Part 16. Synthesis of hexa- and heptaalkyl-substituted inverted or N-confused porphyrins by the '3 + 1' methodology

Journal of Organic Chemistry

Volumn 64, Issue 21, 1999, Pages 7973-7982

  Lash, Timothy D ^a   Richter, Daniel T ^a   Shiner, Craig M ^b  

^a ILLINOIS STATE UNIVERSITY   (United States)

^b MICHIGAN STATE UNIVERSITY   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

ALKYL GROUP; INORGANIC ACID; PORPHYRIN;

ACIDIFICATION; ARTICLE; CHEMICAL REACTION; NUCLEAR MAGNETIC RESONANCE SPECTROSCOPY; OXIDATION; PROTON TRANSPORT; SYNTHESIS;

EID: 0032724266     PISSN: 00223263     EISSN: None     Source Type: Journal    
DOI: 10.1021/jo991019r     Document Type: Article

References (84)

1. Part 15: Lash, T. D.; Romanic, J. L.; Hayes, M. J.; Spence, J. D. Chem. Commun. 1999, 819.
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3. Rothemund, P. J. Am. Chem. Soc. 1935, 57, 2010. Rothemund, P. J. Am. Chem. Soc. 1936, 58, 625. Rothemund, P.; Menotti, A. R. J. Am. Chem. Soc. 1941, 63, 267.
4. Rothemund, P. J. Am. Chem. Soc. 1935, 57, 2010. Rothemund, P. J. Am. Chem. Soc. 1936, 58, 625. Rothemund, P.; Menotti, A. R. J. Am. Chem. Soc. 1941, 63, 267.
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7. Lindsey, J. S.; Schreiman, I. C.; Hsu, H. C.; Kearney, P. C.; Marguerettaz, A. M. J. Org. Chem. 1987, 52, 827. Lindsey, J. S.; Wagner, R. W. J. Org. Chem. 1989, 54, 828. Lindsey, J. S.; MacCrum, K. A.; Tyhonas, J. S.; Chuang, Y.-Y. J. Org. Chem. 1994, 59, 9, 579.
8. Lindsey, J. S.; Schreiman, I. C.; Hsu, H. C.; Kearney, P. C.; Marguerettaz, A. M. J. Org. Chem. 1987, 52, 827. Lindsey, J. S.; Wagner, R. W. J. Org. Chem. 1989, 54, 828. Lindsey, J. S.; MacCrum, K. A.; Tyhonas, J. S.; Chuang, Y.-Y. J. Org. Chem. 1994, 59, 9, 579.
9. Lindsey, J. S.; Schreiman, I. C.; Hsu, H. C.; Kearney, P. C.; Marguerettaz, A. M. J. Org. Chem. 1987, 52, 827. Lindsey, J. S.; Wagner, R. W. J. Org. Chem. 1989, 54, 828. Lindsey, J. S.; MacCrum, K. A.; Tyhonas, J. S.; Chuang, Y.-Y. J. Org. Chem. 1994, 59, 9, 579.
10. Both the Alder-Longo and Lindsey conditions have been adapted for the synthesis of sterically crowded porphyrin systems: Dolphin, D. J. Heterocycl. Chem. 1970, 7, 275. Evans, B.; Smith, K. M.; Fuhrhop, J.-H. Tetrahedron Lett. 1977, 443. Barkigia, K. M.; Berber, M. D.; Fajer, J.; Medforth, C. J.; Renner, M. W.; Smith, K. M. J. Am. Chem. Soc. 1990, 112, 8851. Lash, T. D.; Chandrasekar, P. J. Am. Chem. Soc. 1996, 118, 8767.
11. Both the Alder-Longo and Lindsey conditions have been adapted for the synthesis of sterically crowded porphyrin systems: Dolphin, D. J. Heterocycl. Chem. 1970, 7, 275. Evans, B.; Smith, K. M.; Fuhrhop, J.-H. Tetrahedron Lett. 1977, 443. Barkigia, K. M.; Berber, M. D.; Fajer, J.; Medforth, C. J.; Renner, M. W.; Smith, K. M. J. Am. Chem. Soc. 1990, 112, 8851. Lash, T. D.; Chandrasekar, P. J. Am. Chem. Soc. 1996, 118, 8767.
12. Both the Alder-Longo and Lindsey conditions have been adapted for the synthesis of sterically crowded porphyrin systems: Dolphin, D. J. Heterocycl. Chem. 1970, 7, 275. Evans, B.; Smith, K. M.; Fuhrhop, J.-H. Tetrahedron Lett. 1977, 443. Barkigia, K. M.; Berber, M. D.; Fajer, J.; Medforth, C. J.; Renner, M. W.; Smith, K. M. J. Am. Chem. Soc. 1990, 112, 8851. Lash, T. D.; Chandrasekar, P. J. Am. Chem. Soc. 1996, 118, 8767.
13. Both the Alder-Longo and Lindsey conditions have been adapted for the synthesis of sterically crowded porphyrin systems: Dolphin, D. J. Heterocycl. Chem. 1970, 7, 275. Evans, B.; Smith, K. M.; Fuhrhop, J.-H. Tetrahedron Lett. 1977, 443. Barkigia, K. M.; Berber, M. D.; Fajer, J.; Medforth, C. J.; Renner, M. W.; Smith, K. M. J. Am. Chem. Soc. 1990, 112, 8851. Lash, T. D.; Chandrasekar, P. J. Am. Chem. Soc. 1996, 118, 8767.
14. For other recent syntheses of meso-tetrasubstituted porphyrins, see: Gonsalves, A. M. d'A. R.; Peira, M. M. J. Heterocycl. Chem. 1985, 22, 931. Gonsalves, A. M. d'A. R.; Varejao, J. M. T. B.; Peira, M. M. J. Heterocycl. Chem. 1991, 28, 635. Kuroda, Y.; Murase, H.; Suzuki, Y.; Ogoshi, H. Tetrahedron Lett. 1989, 30, 2411. Onaka, M.; Shinoda, T.; Izumi, Y.; Nolen, E. Chem. Lett. 1993, 117. Laszlo, P.; Luchetti, J. Chem. Lett. 1993, 449. Gradillas, A.; Campo, C. del; Sinisterra, J. V.; Llama, E. F. J. Chem. Soc., Perkin Trans. 1 1995, 2611.
15. For other recent syntheses of meso-tetrasubstituted porphyrins, see: Gonsalves, A. M. d'A. R.; Peira, M. M. J. Heterocycl. Chem. 1985, 22, 931. Gonsalves, A. M. d'A. R.; Varejao, J. M. T. B.; Peira, M. M. J. Heterocycl. Chem. 1991, 28, 635. Kuroda, Y.; Murase, H.; Suzuki, Y.; Ogoshi, H. Tetrahedron Lett. 1989, 30, 2411. Onaka, M.; Shinoda, T.; Izumi, Y.; Nolen, E. Chem. Lett. 1993, 117. Laszlo, P.; Luchetti, J. Chem. Lett. 1993, 449. Gradillas, A.; Campo, C. del; Sinisterra, J. V.; Llama, E. F. J. Chem. Soc., Perkin Trans. 1 1995, 2611.
16. For other recent syntheses of meso-tetrasubstituted porphyrins, see: Gonsalves, A. M. d'A. R.; Peira, M. M. J. Heterocycl. Chem. 1985, 22, 931. Gonsalves, A. M. d'A. R.; Varejao, J. M. T. B.; Peira, M. M. J. Heterocycl. Chem. 1991, 28, 635. Kuroda, Y.; Murase, H.; Suzuki, Y.; Ogoshi, H. Tetrahedron Lett. 1989, 30, 2411. Onaka, M.; Shinoda, T.; Izumi, Y.; Nolen, E. Chem. Lett. 1993, 117. Laszlo, P.; Luchetti, J. Chem. Lett. 1993, 449. Gradillas, A.; Campo, C. del; Sinisterra, J. V.; Llama, E. F. J. Chem. Soc., Perkin Trans. 1 1995, 2611.
17. For other recent syntheses of meso-tetrasubstituted porphyrins, see: Gonsalves, A. M. d'A. R.; Peira, M. M. J. Heterocycl. Chem. 1985, 22, 931. Gonsalves, A. M. d'A. R.; Varejao, J. M. T. B.; Peira, M. M. J. Heterocycl. Chem. 1991, 28, 635. Kuroda, Y.; Murase, H.; Suzuki, Y.; Ogoshi, H. Tetrahedron Lett. 1989, 30, 2411. Onaka, M.; Shinoda, T.; Izumi, Y.; Nolen, E. Chem. Lett. 1993, 117. Laszlo, P.; Luchetti, J. Chem. Lett. 1993, 449. Gradillas, A.; Campo, C. del; Sinisterra, J. V.; Llama, E. F. J. Chem. Soc., Perkin Trans. 1 1995, 2611.
18. For other recent syntheses of meso-tetrasubstituted porphyrins, see: Gonsalves, A. M. d'A. R.; Peira, M. M. J. Heterocycl. Chem. 1985, 22, 931. Gonsalves, A. M. d'A. R.; Varejao, J. M. T. B.; Peira, M. M. J. Heterocycl. Chem. 1991, 28, 635. Kuroda, Y.; Murase, H.; Suzuki, Y.; Ogoshi, H. Tetrahedron Lett. 1989, 30, 2411. Onaka, M.; Shinoda, T.; Izumi, Y.; Nolen, E. Chem. Lett. 1993, 117. Laszlo, P.; Luchetti, J. Chem. Lett. 1993, 449. Gradillas, A.; Campo, C. del; Sinisterra, J. V.; Llama, E. F. J. Chem. Soc., Perkin Trans. 1 1995, 2611.
19. For other recent syntheses of meso-tetrasubstituted porphyrins, see: Gonsalves, A. M. d'A. R.; Peira, M. M. J. Heterocycl. Chem. 1985, 22, 931. Gonsalves, A. M. d'A. R.; Varejao, J. M. T. B.; Peira, M. M. J. Heterocycl. Chem. 1991, 28, 635. Kuroda, Y.; Murase, H.; Suzuki, Y.; Ogoshi, H. Tetrahedron Lett. 1989, 30, 2411. Onaka, M.; Shinoda, T.; Izumi, Y.; Nolen, E. Chem. Lett. 1993, 117. Laszlo, P.; Luchetti, J. Chem. Lett. 1993, 449. Gradillas, A.; Campo, C. del; Sinisterra, J. V.; Llama, E. F. J. Chem. Soc., Perkin Trans. 1 1995, 2611.
20. For a discussion on the preferential formation of porphyrins, rather than oligopyrrolic expanded systems, in a slightly different context, see: Bringmann, G.; Franck, B. Liebigs Ann. Chem. 1982, 1261 and 1272. The selectivity for tetrameric species does not hold true; however, in the synthesis of thiophene-containing analogues of the porphyrins where tetra-and pentathiophene cyclocondensation products are formed by reacting 3,4-diethyl-2-(hydroxymethyl)thiophene with p-toluenesulfonic acid in nitromethane: Vogel, E.; Pohl, M.; Herrmann, A.; Wiss, T.; König, C.; Lex, J.; Gross, M.; Gisselbrecht, J. P. Angew. Chem., Int. Ed. Engl. 1996, 35, 1520. For syntheses of pentaphyrins and hexaphyrins, see: Rexhausen, H.; Gossauer, A. J. Chem. Soc., Chem. Commun. 1983, 275. Gossauer, A. Bull. Soc. Chim. Belg. 1983, 92, 793. Burrell, A. K.; Hemmi, G.; Lynch, V.; Sessler, J. L. J. Am. Chem. Soc. 1991, 113, 4690. Charriere, R.; Jenny, T. A.; Rexhausen, H.; Gossauer, A. Heterocycles 1993, 36, 1561. Very recently, the formation of hexakis(pentafluorophenyl)hexaphyrin from the reaction of pyrrole and pentafluorobenzaldehyde under modified Rothemund conditions (AcOH-PhNO2) has been noted: Neves, M. G. P. M. S.; Martins, R. M.; Tome, A.; Silvestre, A. J. D.; Silva, A. M. S.; Félix, V.; Drew, M. G. B.; Cavaleiro, J. A. S. Chem. Commun. 1999, 385. In unrelated studies, corroles have also been isolated under Rothemund-type conditions: Gross, Z.; Galili, N.; Saltsman, I. Angew. Chemie, Int. Ed. 1999, 38, 1427. Paolesse, R.; Jaquinod, L.; Nurco, D. J.; Mini, S.; Sagone, F.; Boschi, T.; Smith, K. M. Chem. Commun. 1999, 1307.
21. For a discussion on the preferential formation of porphyrins, rather than oligopyrrolic expanded systems, in a slightly different context, see: Bringmann, G.; Franck, B. Liebigs Ann. Chem. 1982, 1261 and 1272. The selectivity for tetrameric species does not hold true; however, in the synthesis of thiophene-containing analogues of the porphyrins where tetra-and pentathiophene cyclocondensation products are formed by reacting 3,4-diethyl-2-(hydroxymethyl)thiophene with p-toluenesulfonic acid in nitromethane: Vogel, E.; Pohl, M.; Herrmann, A.; Wiss, T.; König, C.; Lex, J.; Gross, M.; Gisselbrecht, J. P. Angew. Chem., Int. Ed. Engl. 1996, 35, 1520. For syntheses of pentaphyrins and hexaphyrins, see: Rexhausen, H.; Gossauer, A. J. Chem. Soc., Chem. Commun. 1983, 275. Gossauer, A. Bull. Soc. Chim. Belg. 1983, 92, 793. Burrell, A. K.; Hemmi, G.; Lynch, V.; Sessler, J. L. J. Am. Chem. Soc. 1991, 113, 4690. Charriere, R.; Jenny, T. A.; Rexhausen, H.; Gossauer, A. Heterocycles 1993, 36, 1561. Very recently, the formation of hexakis(pentafluorophenyl)hexaphyrin from the reaction of pyrrole and pentafluorobenzaldehyde under modified Rothemund conditions (AcOH-PhNO2) has been noted: Neves, M. G. P. M. S.; Martins, R. M.; Tome, A.; Silvestre, A. J. D.; Silva, A. M. S.; Félix, V.; Drew, M. G. B.; Cavaleiro, J. A. S. Chem. Commun. 1999, 385. In unrelated studies, corroles have also been isolated under Rothemund-type conditions: Gross, Z.; Galili, N.; Saltsman, I. Angew. Chemie, Int. Ed. 1999, 38, 1427. Paolesse, R.; Jaquinod, L.; Nurco, D. J.; Mini, S.; Sagone, F.; Boschi, T.; Smith, K. M. Chem. Commun. 1999, 1307.
22. For a discussion on the preferential formation of porphyrins, rather than oligopyrrolic expanded systems, in a slightly different context, see: Bringmann, G.; Franck, B. Liebigs Ann. Chem. 1982, 1261 and 1272. The selectivity for tetrameric species does not hold true; however, in the synthesis of thiophene-containing analogues of the porphyrins where tetra-and pentathiophene cyclocondensation products are formed by reacting 3,4-diethyl-2-(hydroxymethyl)thiophene with p-toluenesulfonic acid in nitromethane: Vogel, E.; Pohl, M.; Herrmann, A.; Wiss, T.; König, C.; Lex, J.; Gross, M.; Gisselbrecht, J. P. Angew. Chem., Int. Ed. Engl. 1996, 35, 1520. For syntheses of pentaphyrins and hexaphyrins, see: Rexhausen, H.; Gossauer, A. J. Chem. Soc., Chem. Commun. 1983, 275. Gossauer, A. Bull. Soc. Chim. Belg. 1983, 92, 793. Burrell, A. K.; Hemmi, G.; Lynch, V.; Sessler, J. L. J. Am. Chem. Soc. 1991, 113, 4690. Charriere, R.; Jenny, T. A.; Rexhausen, H.; Gossauer, A. Heterocycles 1993, 36, 1561. Very recently, the formation of hexakis(pentafluorophenyl)hexaphyrin from the reaction of pyrrole and pentafluorobenzaldehyde under modified Rothemund conditions (AcOH-PhNO2) has been noted: Neves, M. G. P. M. S.; Martins, R. M.; Tome, A.; Silvestre, A. J. D.; Silva, A. M. S.; Félix, V.; Drew, M. G. B.; Cavaleiro, J. A. S. Chem. Commun. 1999, 385. In unrelated studies, corroles have also been isolated under Rothemund-type conditions: Gross, Z.; Galili, N.; Saltsman, I. Angew. Chemie, Int. Ed. 1999, 38, 1427. Paolesse, R.; Jaquinod, L.; Nurco, D. J.; Mini, S.; Sagone, F.; Boschi, T.; Smith, K. M. Chem. Commun. 1999, 1307.
23. For a discussion on the preferential formation of porphyrins, rather than oligopyrrolic expanded systems, in a slightly different context, see: Bringmann, G.; Franck, B. Liebigs Ann. Chem. 1982, 1261 and 1272. The selectivity for tetrameric species does not hold true; however, in the synthesis of thiophene-containing analogues of the porphyrins where tetra-and pentathiophene cyclocondensation products are formed by reacting 3,4-diethyl-2-(hydroxymethyl)thiophene with p-toluenesulfonic acid in nitromethane: Vogel, E.; Pohl, M.; Herrmann, A.; Wiss, T.; König, C.; Lex, J.; Gross, M.; Gisselbrecht, J. P. Angew. Chem., Int. Ed. Engl. 1996, 35, 1520. For syntheses of pentaphyrins and hexaphyrins, see: Rexhausen, H.; Gossauer, A. J. Chem. Soc., Chem. Commun. 1983, 275. Gossauer, A. Bull. Soc. Chim. Belg. 1983, 92, 793. Burrell, A. K.; Hemmi, G.; Lynch, V.; Sessler, J. L. J. Am. Chem. Soc. 1991, 113, 4690. Charriere, R.; Jenny, T. A.; Rexhausen, H.; Gossauer, A. Heterocycles 1993, 36, 1561. Very recently, the formation of hexakis(pentafluorophenyl)hexaphyrin from the reaction of pyrrole and pentafluorobenzaldehyde under modified Rothemund conditions (AcOH-PhNO2) has been noted: Neves, M. G. P. M. S.; Martins, R. M.; Tome, A.; Silvestre, A. J. D.; Silva, A. M. S.; Félix, V.; Drew, M. G. B.; Cavaleiro, J. A. S. Chem. Commun. 1999, 385. In unrelated studies, corroles have also been isolated under Rothemund-type conditions: Gross, Z.; Galili, N.; Saltsman, I. Angew. Chemie, Int. Ed. 1999, 38, 1427. Paolesse, R.; Jaquinod, L.; Nurco, D. J.; Mini, S.; Sagone, F.; Boschi, T.; Smith, K. M. Chem. Commun. 1999, 1307.
24. For a discussion on the preferential formation of porphyrins, rather than oligopyrrolic expanded systems, in a slightly different context, see: Bringmann, G.; Franck, B. Liebigs Ann. Chem. 1982, 1261 and 1272. The selectivity for tetrameric species does not hold true; however, in the synthesis of thiophene-containing analogues of the porphyrins where tetra-and pentathiophene cyclocondensation products are formed by reacting 3,4-diethyl-2-(hydroxymethyl)thiophene with p-toluenesulfonic acid in nitromethane: Vogel, E.; Pohl, M.; Herrmann, A.; Wiss, T.; König, C.; Lex, J.; Gross, M.; Gisselbrecht, J. P. Angew. Chem., Int. Ed. Engl. 1996, 35, 1520. For syntheses of pentaphyrins and hexaphyrins, see: Rexhausen, H.; Gossauer, A. J. Chem. Soc., Chem. Commun. 1983, 275. Gossauer, A. Bull. Soc. Chim. Belg. 1983, 92, 793. Burrell, A. K.; Hemmi, G.; Lynch, V.; Sessler, J. L. J. Am. Chem. Soc. 1991, 113, 4690. Charriere, R.; Jenny, T. A.; Rexhausen, H.; Gossauer, A. Heterocycles 1993, 36, 1561. Very recently, the formation of hexakis(pentafluorophenyl)hexaphyrin from the reaction of pyrrole and pentafluorobenzaldehyde under modified Rothemund conditions (AcOH-PhNO2) has been noted: Neves, M. G. P. M. S.; Martins, R. M.; Tome, A.; Silvestre, A. J. D.; Silva, A. M. S.; Félix, V.; Drew, M. G. B.; Cavaleiro, J. A. S. Chem. Commun. 1999, 385. In unrelated studies, corroles have also been isolated under Rothemund-type conditions: Gross, Z.; Galili, N.; Saltsman, I. Angew. Chemie, Int. Ed. 1999, 38, 1427. Paolesse, R.; Jaquinod, L.; Nurco, D. J.; Mini, S.; Sagone, F.; Boschi, T.; Smith, K. M. Chem. Commun. 1999, 1307.
25. For a discussion on the preferential formation of porphyrins, rather than oligopyrrolic expanded systems, in a slightly different context, see: Bringmann, G.; Franck, B. Liebigs Ann. Chem. 1982, 1261 and 1272. The selectivity for tetrameric species does not hold true; however, in the synthesis of thiophene-containing analogues of the porphyrins where tetra-and pentathiophene cyclocondensation products are formed by reacting 3,4-diethyl-2-(hydroxymethyl)thiophene with p-toluenesulfonic acid in nitromethane: Vogel, E.; Pohl, M.; Herrmann, A.; Wiss, T.; König, C.; Lex, J.; Gross, M.; Gisselbrecht, J. P. Angew. Chem., Int. Ed. Engl. 1996, 35, 1520. For syntheses of pentaphyrins and hexaphyrins, see: Rexhausen, H.; Gossauer, A. J. Chem. Soc., Chem. Commun. 1983, 275. Gossauer, A. Bull. Soc. Chim. Belg. 1983, 92, 793. Burrell, A. K.; Hemmi, G.; Lynch, V.; Sessler, J. L. J. Am. Chem. Soc. 1991, 113, 4690. Charriere, R.; Jenny, T. A.; Rexhausen, H.; Gossauer, A. Heterocycles 1993, 36, 1561. Very recently, the formation of hexakis(pentafluorophenyl)hexaphyrin from the reaction of pyrrole and pentafluorobenzaldehyde under modified Rothemund conditions (AcOH-PhNO2) has been noted: Neves, M. G. P. M. S.; Martins, R. M.; Tome, A.; Silvestre, A. J. D.; Silva, A. M. S.; Félix, V.; Drew, M. G. B.; Cavaleiro, J. A. S. Chem. Commun. 1999, 385. In unrelated studies, corroles have also been isolated under Rothemund-type conditions: Gross, Z.; Galili, N.; Saltsman, I. Angew. Chemie, Int. Ed. 1999, 38, 1427. Paolesse, R.; Jaquinod, L.; Nurco, D. J.; Mini, S.; Sagone, F.; Boschi, T.; Smith, K. M. Chem. Commun. 1999, 1307.
26. For a discussion on the preferential formation of porphyrins, rather than oligopyrrolic expanded systems, in a slightly different context, see: Bringmann, G.; Franck, B. Liebigs Ann. Chem. 1982, 1261 and 1272. The selectivity for tetrameric species does not hold true; however, in the synthesis of thiophene-containing analogues of the porphyrins where tetra-and pentathiophene cyclocondensation products are formed by reacting 3,4-diethyl-2-(hydroxymethyl)thiophene with p-toluenesulfonic acid in nitromethane: Vogel, E.; Pohl, M.; Herrmann, A.; Wiss, T.; König, C.; Lex, J.; Gross, M.; Gisselbrecht, J. P. Angew. Chem., Int. Ed. Engl. 1996, 35, 1520. For syntheses of pentaphyrins and hexaphyrins, see: Rexhausen, H.; Gossauer, A. J. Chem. Soc., Chem. Commun. 1983, 275. Gossauer, A. Bull. Soc. Chim. Belg. 1983, 92, 793. Burrell, A. K.; Hemmi, G.; Lynch, V.; Sessler, J. L. J. Am. Chem. Soc. 1991, 113, 4690. Charriere, R.; Jenny, T. A.; Rexhausen, H.; Gossauer, A. Heterocycles 1993, 36, 1561. Very recently, the formation of hexakis(pentafluorophenyl)hexaphyrin from the reaction of pyrrole and pentafluorobenzaldehyde under modified Rothemund conditions (AcOH-PhNO2) has been noted: Neves, M. G. P. M. S.; Martins, R. M.; Tome, A.; Silvestre, A. J. D.; Silva, A. M. S.; Félix, V.; Drew, M. G. B.; Cavaleiro, J. A. S. Chem. Commun. 1999, 385. In unrelated studies, corroles have also been isolated under Rothemund-type conditions: Gross, Z.; Galili, N.; Saltsman, I. Angew. Chemie, Int. Ed. 1999, 38, 1427. Paolesse, R.; Jaquinod, L.; Nurco, D. J.; Mini, S.; Sagone, F.; Boschi, T.; Smith, K. M. Chem. Commun. 1999, 1307.
27. For a discussion on the preferential formation of porphyrins, rather than oligopyrrolic expanded systems, in a slightly different context, see: Bringmann, G.; Franck, B. Liebigs Ann. Chem. 1982, 1261 and 1272. The selectivity for tetrameric species does not hold true; however, in the synthesis of thiophene-containing analogues of the porphyrins where tetra-and pentathiophene cyclocondensation products are formed by reacting 3,4-diethyl-2-(hydroxymethyl)thiophene with p-toluenesulfonic acid in nitromethane: Vogel, E.; Pohl, M.; Herrmann, A.; Wiss, T.; König, C.; Lex, J.; Gross, M.; Gisselbrecht, J. P. Angew. Chem., Int. Ed. Engl. 1996, 35, 1520. For syntheses of pentaphyrins and hexaphyrins, see: Rexhausen, H.; Gossauer, A. J. Chem. Soc., Chem. Commun. 1983, 275. Gossauer, A. Bull. Soc. Chim. Belg. 1983, 92, 793. Burrell, A. K.; Hemmi, G.; Lynch, V.; Sessler, J. L. J. Am. Chem. Soc. 1991, 113, 4690. Charriere, R.; Jenny, T. A.; Rexhausen, H.; Gossauer, A. Heterocycles 1993, 36, 1561. Very recently, the formation of hexakis(pentafluorophenyl)hexaphyrin from the reaction of pyrrole and pentafluorobenzaldehyde under modified Rothemund conditions (AcOH-PhNO2) has been noted: Neves, M. G. P. M. S.; Martins, R. M.; Tome, A.; Silvestre, A. J. D.; Silva, A. M. S.; Félix, V.; Drew, M. G. B.; Cavaleiro, J. A. S. Chem. Commun. 1999, 385. In unrelated studies, corroles have also been isolated under Rothemund-type conditions: Gross, Z.; Galili, N.; Saltsman, I. Angew. Chemie, Int. Ed. 1999, 38, 1427. Paolesse, R.; Jaquinod, L.; Nurco, D. J.; Mini, S.; Sagone, F.; Boschi, T.; Smith, K. M. Chem. Commun. 1999, 1307.
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