Triflate-subphthalocyanines: Versatile, reactive intermediates for axial functionalization at the boron atom

Angewandte Chemie - International Edition

Volumn 50, Issue 15, 2011, Pages 3506-3509

  Guilleme, Julia ^a   González Rodríguez, David ^a   Torres, Tomas ^a,b  

^a UNIVERSIDAD AUTÓNOMA DE MADRID   (Spain)

^b INSTITUTO MADRILEÑO DE ESTUDIOS AVANZADOS EN NANOCIENCIA IMDEA NANOCIENCIA   (Spain)

Author keywords

boron; nucleophilic substitution; phthalocyanines; subazamacrocycles; subphthalocyanine

Indexed keywords

BORON ATOM; CARBON NUCLEOPHILES; FUNCTIONALIZATIONS; NUCLEOPHILIC SUBSTITUTION; PHTHALOCYANINES; REACTIVE INTERMEDIATE; SUBAZAMACROCYCLES; SUBPHTHALOCYANINES; TRIFLATES;

BORON; ISOMERS; NITROGEN COMPOUNDS; OXYGEN; SUBSTITUTION REACTIONS; SULFUR;

BORON COMPOUNDS;

EID: 79953246833     PISSN: 14337851     EISSN: 15213773     Source Type: Journal    
DOI: 10.1002/anie.201007240     Document Type: Article

References (45)

1. C. Spiteri, J. E. Moses, Angew. Chem. 2010, 122, 33-36
2. Angew. Chem. Int. Ed. 2010, 49, 31-33
3. C. E. Hoyle, C. N. Bowman, Angew. Chem. 2010, 122, 1584-1617
4. Angew. Chem. Int. Ed. 2010, 49, 1540-1573.
5. B. J. Ravoo, J. Mater. Chem. 2009, 19, 8902-8906
6. B. S. Sumerlin, A. P. Vogt, Macromolecules 2010, 43, 1-13
7. S. K. Mamidyala, M. G. Finn, Chem. Soc. Rev. 2010, 39, 1252-1261
8. A. B. Lowe, C. E. Hoyle, C. N. Bowman, J. Mater. Chem. 2010, 20, 4745-4750.
9. C. G. Claessens, W. J. Blau, M. J. Cook, M. Hanack, R. J. M. Nolte, T. Torres, D. Wöhrle, Monatsh. Chem. 2001, 132, 3-11
10. C. G. Claessens, D. González-Rodríguez, T. Torres, Chem. Rev. 2002, 102, 835-853
11. N. Kobayashi, in The Porphyrin Handbook, Vol. 15 (Eds.:, K. M. Kadish, K. M. Smith, R. Guillard,), Academic Press, San Diego, 2003, p. 15
12. T. Torres, Angew. Chem. 2006, 118, 2900-2903
13. Angew. Chem. Int. Ed. 2006, 45, 2834-2837
14. Y. Inokuma, A. Osuka, Dalton Trans. 2008, 2517-2526
15. P. J. Brothers, Chem. Commun. 2008, 2090-2102
16. C. G. Claessens, A. Medina, J. Porphyrins Phthalocyanines 2009, 13, 446-454.
17. Submacrocycles are versatile active chromophores that can function as energy donors (Refs. [7a,b,d,g]), energy acceptors (Ref. [7e]) electron donors (Refs. [7a,d]), or electron acceptors (Refs. [7b,c,h]): a) D. González-Rodríguez, T. Torres, D. M. Guldi, J. Rivera, M. A. Herranz, L. Echegoyen, J. Am. Chem. Soc. 2004, 126, 6301-6313
18. D. González-Rodríguez, C. G. Claessens, T. Torres, S.-G. Liu, L. Echegoyen, N. Vila, S. Nonell, Chem. Eur. J. 2005, 11, 3881-3893
19. D. González-Rodríguez, T. Torres, M. M. Olmstead, J. Rivera, M. A. Herranz, L. Echegoyen, C. Atienza Castellanos, D. M. Guldi, J. Am. Chem. Soc. 2006, 128, 10680-10681
20. D. González-Rodríguez, T. Torres, M. A. Herranz, L. Echegoyen, E. Carbonell, D. M. Guldi, Chem. Eur. J. 2008, 14, 7670-7679
21. J.-Y. Liu, H.-S. Yeung, W. Xu, X. Li, D. K. P. Ng, Org. Lett. 2008, 10, 5421-5424
22. Y. Inokuma, S. Easwaramoorthi, Z. Seok Yoon, D. Kim, A. Osuka, J. Am. Chem. Soc. 2008, 130, 12234-12235
23. R. Ziessel, G. Ulrich, K. J. Elliott, A. Harriman, Chem. Eur. J. 2009, 15, 4980-4984
24. M. E. El-Khouly, J. B. Ryu, K.-Y. Kay, O. Ito, S. Fukuzumi, J. Phys. Chem. C 2009, 113, 15444-15453
25. D. González-Rodríguez, E. Carbonell, D. M. Guldi, T. Torres, Angew. Chem. 2009, 121, 8176-8180
26. Angew. Chem. Int. Ed. 2009, 48, 8032-8036
27. D. González-Rodríguez, E. Carbonell, G. de Miguel Rojas, C. Atienza Castellanos, D. M. Guldi, T. Torres, J. Am. Chem. Soc. 2010, 132, 16488-16500.
28. R. A. Kipp, J. A. Simon, M. Beggs, H. E. Ensley, R. H. Schmehl, J. Phys. Chem. A 1998, 102, 5659-5664.
29. E. Tsurumaki, Y. Inokuma, S. Easwaramoorthi, J. Min Lim, D. Kim, A. Osuka, Chem. Eur. J. 2009, 15, 237-247
30. D. González-Rodríguez, T. Torres, Eur. J. Org. Chem. 2009, 1871-1879
31. S. Hayashi, Y. Inokuma, S. Easwaramoorthi, K. Suk Kim, D. Kim, A. Osuka, Angew. Chem. 2010, 122, 331-334
32. Angew. Chem. Int. Ed. 2010, 49, 321-324
33. Angew. Chem. 2010, 122, 331-334.
34. C. G. Claessens, D. González-Rodríguez, B. del Rey, T. Torres, G. Mark, H.-P. Schuchmann, C. von Sonntag, J. G. MacDonald, R. S. Nohr, Eur. J. Org. Chem. 2003, 2547-2551
35. N. Shibata, B. Das, E. Tokunaga, M. Shiro, N. Kobayashi, Chem. Eur. J. 2010, 16, 7554-7562.
36. T. Kato, F. S. Tham, P. D. W. Boyd, C. A. Reed, Heteroat. Chem. 2006, 17, 209-216.
37. See the Supporting Information for further details.
38. Likely formed by reaction between SubPcBOH and SubPcBOTf. See a) M. Geyer, F. Plenzig, J. Rauschnabel, M. Hanack, B. del Rey, A. Sastre, T. Torres, Synthesis 1996, 1139
39. N. Kobayashi, T. Ishizaki, K. Ishii, H. Konami, J. Am. Chem. Soc. 1999, 121, 9096-9110.
40. The yields reported in Tables 1 and 2 were calculated with respect to the starting SubPcBCl. It is important to note that the yields calculated with respect to the nucleophile are close to quantitative when an excess of SubPcBOTf is employed, which renders this method ideal for the complete derivatization of systems with multiple functionalizable sites, such as polymers or reactive surfaces.
41. The reaction of SubPcBCl with alkynyl magnesium bromides was studied recently, see:, F. Camerel, G. Ulrich, P. Retailleau, R. Ziessel, Angew. Chem. 2008, 120, 9008-9012
42. Angew. Chem. Int. Ed. 2008, 47, 8876-8880.
43. 3 and DBU. It could also be detected in the reaction between SubPcBCl and PhLi, but the yield was very low. X-ray diffraction showed an axial B-C distance of 1.605 Å. See ref. [10a].
44. CCDC 798228, 798229, 798230, 798231 and 798232 contain the supplementary crystallographic data for this paper. These data can be obtained free of charge from The Cambridge Crystallographic Data Centre via.
45. 3SiOTf, to generate activated triflate-SubP intermediates.