Synthesis of [28]heptaphyrin(1.0.0.1.0.0.0) and [32]Octaphyrin(1.0.0.0.1.0.0.0) via a directed oxidative ring closure: The first expanded porphyrins containing a quaterpyrrole subunit [18]

Journal of the American Chemical Society

Volumn 121, Issue 48, 1999, Pages 11257-11258

  Sessler, Jonathan L ^a   Seidel, Daniel ^a   Lynch, Vincent ^a  

^a UNIVERSITY OF TEXAS AT AUSTIN   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

MACROCYCLIC COMPOUND; PORPHYRIN DERIVATIVE; PYRROLE DERIVATIVE; UNCLASSIFIED DRUG; [28]HEPTAPHYRIN(1.0.0.1.0.0.0); [32]OCTAPHYRIN(1.0.0.0.1.0.0.0);

CATALYSIS; LETTER; OXIDATION; POLYMERIZATION; SYNTHESIS; X RAY DIFFRACTION;

EID: 0033537021     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja992934x     Document Type: Letter

References (30)

1. (a) Sessler, J. L.; Weghorn, S. J. Expanded, Contracted, and Isomeric Porphyrins; Elsevier: Oxford, 1997.
2. (b) Jasat, A.; Dolphin, D. Chem. Rev. 1997, 97, 2267-2340.
3. (c) Sessler, J. L.; Gebauer, A.; Weghorn, S. J. In The Porphyrin Handbook; Kadish, K., Smith, K. M., Guilard, R., Eds.; Academic Press: San Diego, 1999, in press.
4. For recent examples of expanded porphyrins prepared using Rothemund-like chemistry, see: (a) Neves, M. G. P. M. S.; Martins, R. M.; Tomé, A. C.; Silvestre, A. J. D.; Silva, A. M. S.; Félix, V.; Drew, M. G. B., Cavaleiro, J. A. S. Chem. Soc. Chem. Commun. 1999, 385-386. (b) Setsune, J.; Katakami, Y.; Iizuna, N. J. Am. Chem. Soc. 1999, 121, 8957-8958. See also ref 6.
5. For recent examples of expanded porphyrins prepared using Rothemund-like chemistry, see: (a) Neves, M. G. P. M. S.; Martins, R. M.; Tomé, A. C.; Silvestre, A. J. D.; Silva, A. M. S.; Félix, V.; Drew, M. G. B., Cavaleiro, J. A. S. Chem. Soc. Chem. Commun. 1999, 385-386. (b) Setsune, J.; Katakami, Y.; Iizuna, N. J. Am. Chem. Soc. 1999, 121, 8957-8958. See also ref 6.
6. For recent examples of expanded porphyrins prepared using MacDonald-like chemistry, see: (a) Srinivasan, A.; Pushpan, S. K.; Ravikumar, M.; Chandrashekar, T. K.; Roy, R. Tetrahedron 1999, 55, 6671-6680. (b) Srinivasan, A.; Pushpan, S. K.; Kumar, M. R.; Mahajan, S.; Chandrashekar, T. K., Roy, R.; Ramamurthy, P. J. Chem. Soc., Perkin Trans. 2, 1999, 961-968. (c) Michels, M.; Zander, L.; Wytko, J. Abstracts of the 24th International Symposium on Macrocyclic Chemistry (Barcelona), July 1999.
7. For recent examples of expanded porphyrins prepared using MacDonald-like chemistry, see: (a) Srinivasan, A.; Pushpan, S. K.; Ravikumar, M.; Chandrashekar, T. K.; Roy, R. Tetrahedron 1999, 55, 6671-6680. (b) Srinivasan, A.; Pushpan, S. K.; Kumar, M. R.; Mahajan, S.; Chandrashekar, T. K., Roy, R.; Ramamurthy, P. J. Chem. Soc., Perkin Trans. 2, 1999, 961-968. (c) Michels, M.; Zander, L.; Wytko, J. Abstracts of the 24th International Symposium on Macrocyclic Chemistry (Barcelona), July 1999.
8. For recent examples of expanded porphyrins prepared using MacDonald-like chemistry, see: (a) Srinivasan, A.; Pushpan, S. K.; Ravikumar, M.; Chandrashekar, T. K.; Roy, R. Tetrahedron 1999, 55, 6671-6680. (b) Srinivasan, A.; Pushpan, S. K.; Kumar, M. R.; Mahajan, S.; Chandrashekar, T. K., Roy, R.; Ramamurthy, P. J. Chem. Soc., Perkin Trans. 2, 1999, 961-968. (c) Michels, M.; Zander, L.; Wytko, J. Abstracts of the 24th International Symposium on Macrocyclic Chemistry (Barcelona), July 1999.
9. Ikeda, H.; Sessler J. L. J. Org. Chem. 1993, 58, 2340-2342.
10. Ikeda, H.; Hoehner, M.; Sessler, J. L., unpublished results.
11. For recent examples of Rothemund-like coupling procedures wherein oxidative couplings are implicated in the formation of expanded porphyrin products, see: (a) Rachlewicz, K.; Sprutta, N.; Chmielewski, P. J.; Latos-Grazynski, L. J. Chem. Soc., Perkin Trans. 2, 1998, 969-975. (b) Narayanan, S. J.; Sridevi, B.; Chandrashekar, T. K.; Vij, A.; Roy, R. Angew. Chem., Int. Ed. 1998, 37, 3394-3397. (c) Gross, Z.; Galili, N.; Saltsman, I. Angew. Chem., Int. Ed. 1999, 38, 1427-1429. (d) Paolesse, R.; Jaquinod, L.; Nurco, D. J.; Mini, S.; Sagone, F.; Boschi, T.; Smith, K. M. J. Chem. Soc., Chem. Commun. 1999, 1307-1308.
12. For recent examples of Rothemund-like coupling procedures wherein oxidative couplings are implicated in the formation of expanded porphyrin products, see: (a) Rachlewicz, K.; Sprutta, N.; Chmielewski, P. J.; Latos-Grazynski, L. J. Chem. Soc., Perkin Trans. 2, 1998, 969-975. (b) Narayanan, S. J.; Sridevi, B.; Chandrashekar, T. K.; Vij, A.; Roy, R. Angew. Chem., Int. Ed. 1998, 37, 3394-3397. (c) Gross, Z.; Galili, N.; Saltsman, I. Angew. Chem., Int. Ed. 1999, 38, 1427-1429. (d) Paolesse, R.; Jaquinod, L.; Nurco, D. J.; Mini, S.; Sagone, F.; Boschi, T.; Smith, K. M. J. Chem. Soc., Chem. Commun. 1999, 1307-1308.
13. For recent examples of Rothemund-like coupling procedures wherein oxidative couplings are implicated in the formation of expanded porphyrin products, see: (a) Rachlewicz, K.; Sprutta, N.; Chmielewski, P. J.; Latos-Grazynski, L. J. Chem. Soc., Perkin Trans. 2, 1998, 969-975. (b) Narayanan, S. J.; Sridevi, B.; Chandrashekar, T. K.; Vij, A.; Roy, R. Angew. Chem., Int. Ed. 1998, 37, 3394-3397. (c) Gross, Z.; Galili, N.; Saltsman, I. Angew. Chem., Int. Ed. 1999, 38, 1427-1429. (d) Paolesse, R.; Jaquinod, L.; Nurco, D. J.; Mini, S.; Sagone, F.; Boschi, T.; Smith, K. M. J. Chem. Soc., Chem. Commun. 1999, 1307-1308.
14. For recent examples of Rothemund-like coupling procedures wherein oxidative couplings are implicated in the formation of expanded porphyrin products, see: (a) Rachlewicz, K.; Sprutta, N.; Chmielewski, P. J.; Latos-Grazynski, L. J. Chem. Soc., Perkin Trans. 2, 1998, 969-975. (b) Narayanan, S. J.; Sridevi, B.; Chandrashekar, T. K.; Vij, A.; Roy, R. Angew. Chem., Int. Ed. 1998, 37, 3394-3397. (c) Gross, Z.; Galili, N.; Saltsman, I. Angew. Chem., Int. Ed. 1999, 38, 1427-1429. (d) Paolesse, R.; Jaquinod, L.; Nurco, D. J.; Mini, S.; Sagone, F.; Boschi, T.; Smith, K. M. J. Chem. Soc., Chem. Commun. 1999, 1307-1308.
15. Falk, H.; Flödl, H. Monatsh. Chem. 1988, 119, 247-252.
16. The use of an oxidative coupling strategy to produce sapphyrin has recently been reported: Paolesse, R.; Licoccia, S.; Spagnoli, M.; Boschi, T.; Khoury, R. G.; Smith, K. M. J. Org. Chem. 1997, 62, 5133-5137.
17. (a) While this manuscript was being prepared for publication, we became aware of a report wherein an oxidative coupling procedure was used to prepare heterosmaragdyrins; see: Narayanan, S. J.; Sridevi, B.; Chandrashekar, T. K.; Englich, U.; Ruhlandt-Senge, K. Org. Lett. 1999, 1, 587-590. (b) After this paper was submitted for publication and accepted subject to minor revisions, a report appeared detailing the use of an oxidative coupling to produce an expanded, tetrapyrrolic corrole: Paolesse, R.; Khoury, R. G.; Sala, F. D.; Natale, C. D.; Sagone, F.; Smith, K. Angew. Chem., Int. Ed. 1999, 38, 2577-2578.
18. (a) While this manuscript was being prepared for publication, we became aware of a report wherein an oxidative coupling procedure was used to prepare heterosmaragdyrins; see: Narayanan, S. J.; Sridevi, B.; Chandrashekar, T. K.; Englich, U.; Ruhlandt-Senge, K. Org. Lett. 1999, 1, 587-590. (b) After this paper was submitted for publication and accepted subject to minor revisions, a report appeared detailing the use of an oxidative coupling to produce an expanded, tetrapyrrolic corrole: Paolesse, R.; Khoury, R. G.; Sala, F. D.; Natale, C. D.; Sagone, F.; Smith, K. Angew. Chem., Int. Ed. 1999, 38, 2577-2578.
19. Meyer, S.; Andrioletti, B.; Sessler, J. L.; Lynch V. J. Org. Chem. 1998, 63, 6752-6756.
20. Sessler, J. L.; Hoehner, M. C. Synlett 1994, 211-212.
21. A derivative of 4 has recently been reported; see: Morosini, P.; Scherer, M.; Meyer, S.; Lynch V.; Sessler, J. L. J. Org. Chem. 1997, 62, 8848-8853.
22. While, to the best of our knowledge, 7 is a new compound, unsubstituted tetrapyrroles of this type are known; see: Sepulveda-Boza, S.; Braitmaier, E. Liebigs Ann. Chem. 1983, 894-896.
23. The octaethyl-substituted form of 7 is also known, see: Bröring, M.; Jendrny, J.; Zander, L.; Schmickler, H.; Lex, J.; Wu, Y.-D.; Nendel, M.; Chen, J.; Plattner, D. A.; Houk, K. N.; Vogel, E. Angew. Chem., Int. Ed. Eng. 1995, 34, 2515-2517.
24. When DDQ or molecular oxygen were used as the oxidants, more complex product mixtures were obtained wherein 6 was still present, albeit in lower yield.
25. Sessler, J. L.; Weghorn, S. J.; Hiseada, Y.; Lynch, V. Chem. Eur. J. 1995, 1, 56-67.
26. max (ε) values of 507 nm (56400), 613 nm (53000), 526 nm (41 500), and ∼660 nm (sh), respectively. See the Supporting Information.
27. w = 0.242, with a conventional R = 0.101. See Supporting Information for details.
28. Anion binding in protonated expanded porphyrins is now well established; cf. Sessler, J. L.; Sansom, P. I.; Andrievsky, A.; Král, V. In Supramolecular Chemistry of Anions; Bianchi, A., Bowman-James, K., Garcia-Espana, E., Eds.; VCH Verlag; Weinheim, 1997; pp. 355-419. See also ref 1.
29. Vogel, E.; Bröring, M.; Fink, J.; Rosen, D.; Schmickler, H.; Lex, J.; Chan, K. W. K.; Wu, Y.-D.; Plattner, D. A.; Nendel, M.; Houk, K. N. Angew. Chem., Int. Ed. Eng. 1995, 34, 2511-2514.
30. In addition to the [28]heptaphyrin(1.0.0.1.0.0.0) (5) and [32]octaphyrin-(1.0.0.0.1.0.0.0) (6) products reported here, we have succeeded in preparing an alkyl-substituted [24]hexaphyrin(1.0.1.0.0.0) from an appropriate linear hexapyrrolic precursor.