Photochemistry of an azido-functionalized cryptand: Controlling the reactivity of an extremely long-lived singlet aryl nitrene by complexation to alkali cations

Journal of the American Chemical Society

Volumn 127, Issue 18, 2005, Pages 6883-6892

  Bucher, Götz ^a   Tönshoff, Christina ^a   Nicolaides, Athanassios ^b  

^a RUHR UNIVERSITY BOCHUM   (Germany)

^b UNIVERSITY OF CYPRUS   (Cyprus)

Author keywords

[No Author keywords available]

Indexed keywords

ABSORPTION; ACETONITRILE; AMINES; COMPLEXATION; DERIVATIVES; LASER APPLICATIONS; PHOTOLYSIS; POSITIVE IONS; POTASSIUM; QUANTUM THEORY; SODIUM; SOLUTIONS; SUBSTITUTION REACTIONS; ULTRAVIOLET SPECTROSCOPY;

ARYL NITRENE; AZIDO-FUNCTIONALIZED CRYPTAND; LASER FLASH PHOTOLYSIS (LFP); QUANTUM MECHANICAL CALCULATIONS;

NITROGEN COMPOUNDS;

2 IMINOQUINONE METHIDE; ACETONITRILE DERIVATIVE; ALDEHYDE DERIVATIVE; ALKALI; AMINOBENZALDEHYDE; ANILINE DERIVATIVE; AZEPINE DERIVATIVE; CATION; DIDEHYDROAZEPINE; DIETHYLAMINE; LIGAND; METHYLENE AZEPINE; POTASSIUM DERIVATIVE; QUINONE DERIVATIVE; SODIUM DERIVATIVE; UNCLASSIFIED DRUG; WATER;

ARTICLE; COMPLEX FORMATION; ELECTRON SPIN RESONANCE; ENVIRONMENTAL TEMPERATURE; LASER; LOW TEMPERATURE; PHOTOCHEMISTRY; PHOTOLYSIS; QUANTUM MECHANICS; ULTRAVIOLET SPECTROSCOPY;

EID: 18644378491     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja0447208     Document Type: Article

References (56)

1. Platz, M. S. Acc. Chem. Res. 1995, 28, 487.
2. Schuster, G. B.; Platz, M. S. In Advances in Photochemistry; D. H. Volman, G. Hammond, D. C. Neckers, Eds.; John Wiley & Sons: New York, 1992; pp 69-143.
3. (a) Bucher, G. Photochemical Reactivity of Azides. In CRC Handbook of Photochemistry, 2nd ed.; CRC Press: Boca Raton, 2003; Chapter 44.
4. (b) Platz, M. S. Nitrenes. In Reactive Intermediate Chemistry; Wiley-Interscience: Hoboken, 2004; Chapter 11.
5. (c) Doyle, M. P. Synthetic Carbene and Nitrene Chemistry. In Reactive Intermediate Chemistry; Wiley Interscience: Hoboken, 2004; Chapter 12.
6. (d) Tokitoh, N.; Saiki, T.; Okazaki, R. Chem. Commun. 1995, 1899.
7. Gritsan, N. P.; Yuzawa, T.; Platz, M. S. J. Am. Chem. Soc. 1997, 119, 5059.
8. Born, R.; Burda, C.; Senn, P.; Wirz, J. J. Am. Chem. Soc. 1997, 119, 5061.
9. Leyva, E.; Platz, M. S.; Persy, G.; Wirz, J. J. Am. Chem. Soc. 1986, 108, 3783.
10. Hayes, J. C.; Sheridan, R. S. J. Am. Chem. Soc. 1990, 112, 5879.
11. Bucher, G.; Scaiano, J. C.; Sinta, R.; Barclay, G.; Cameron, J. J. Am. Chem. Soc. 1995, 117, 3848.
12. McClelland, R. A.; Davidse, P. A.; Hadzialic, G. J. Am. Chem. Soc. 1995, 117, 4173.
13. McClelland, R. A.; Kahley, M. J.; Davidse, A.; Hadzialic, G. J. Am. Chem. Soc. 1996, 118, 4794.
14. Plenio, H.; Diodone, R. Angew. Chem. 1994, 106, 2267;
15. Plenio, H.; Diodone, R. Angew. Chem., Int. Ed. 1994, 33, 2175.
16. Plenio, H.; Diodone, R. J. Am. Chem. Soc. 1996, 118, 356.
17. Tönshoff, C.; Merz, K.; Bucher, G. Org. Biomol. Chem. 2005, 303.
18. Bucher, G. Eur. J. Org. Chem. 2001, 2463.
19. Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Scuseria, G. E.; Robb, M. A.; Cheeseman, J. R.; Zakrzewski, V. G.; Montgomery, J. A., Jr.; Stratmann, R. E.; Burant, J. C.; Dapprich, S.; Millam, J. M.; Daniels, A. D.; Kudin, K. N.; Strain, M. C.; Farkas, O.; Tomasi, J.; Barone, V.; Cossi, M.; Cammi, R.; Mennucci, B.; Pomelli, C.; Adamo, C.; Clifford, S.; Ochterski, J.; Petersson, G. A.; Ayala, P. Y.; Cui, Q.; Morokuma, K.; Malick, D. K.; Rabuck, A. D.; Raghavachari, K.; Foresman, J. B.; Cioslowski, J.; Ortiz, J. V.; Baboul, A. G.; Stefanov, B. B.; Liu, G.; Liashenko, A.; Piskorz, P.; Komaromi, I.; Gomperts, R.; Martin, R. L.; Fox, D. J.; Keith, T.; Al-Laham, M. A.; Peng, C. Y.; Nanayakkara, A.; Gonzalez, C.; Challacombe, M.; Gill, P. M. W.; Johnson, B.; Chen, W.; Wong, M. W.; Andres, J. L.; Gonzalez, C.; Head-Gordon, M.; Replogle, E. S.; Pople, J. A. Gaussian 98, Revision A.9; Gaussian, Inc.: Pittsburgh, PA, 1998.
20. Schmidt, M. W.; Baldridge, K. K.; Boats, J. A.; Elbert, S. T.; Gordon, M. S.; Jensen, J. H.; Koseki, S.; Matsunaga, N.; Nguyen, K. A.; Su, S.; Windus, T. L.; Dupuis, M.; Montgomery, J. A., Jr. J. Comput. Chem. 1993, 14, 1347.
21. Bucher, G. Angew. Chem. 1999, 111, 1247;
22. Bucher, G. Angew. Chem., Int. Ed. 1999, 38, 1192.
23. DeGraff, B. A.; Gillespie, D. W.; Sundberg, R. J. J. Am. Chem. Soc. 1974, 96, 7491.
24. Bucher, G. Eur. J. Org. Chem. 2001, 2447.
25. B3LYP/6-31G(d).
26. exo-Attack, formation of the 2-cyanotetrahydroquinoline derivative. Simpler iminoquinone methides, as described in ref 14, are considerably more reactive toward dienophiles. The reason for the significantly reduced reactivity of Z-9 is unclear at present. Most likely, steric factors play a role.
27. (a) Smolinsky, G.; Wasserman, E.; Yager, Y. A. J. Am. Chem. Soc. 1962, 84, 3220.
28. (b) The signals at -3400 G are narrow triplets, which are assigned to aminyl/alkyl radical pairs formed by intramolecular hydrogen abstraction by the nitrene from a crown ether methylene group.
29. +.
30. 32 must be destabilized by the electron-rich environment, or else the didehydroazepine 7 stabilized, or both.
31. (b) Hrovat, D. A.; Waali, E. E.; Borden, W. T. J. Am. Chem. Soc. 1992, 114, 8698.
32. Kim, S.-J.; Hamilton, T. P.; Schaefer, H. F., III. J. Am. Chem. Soc. 1992, 114, 5349
33. Karney, W. L.; Borden, W. T. J. Am. Chem. Soc. 1997, 119, 1378.
34. Gritsan, N. P.; Zhu, Z.; Hadad, C. M.; Platz, M. S. J. Am. Chem. Soc. 1999, 121, 1202.
35. Morawietz, J.; Sander, W. J. Org. Chem. 1996, 61, 4351.
36. Tsao, M.-L.; Gritsan, N.; James, T. R.; Platz, M. S.; Hrovat, D. A.; Borden, W. T. J. Am. Chem. Soc. 2003, 125, 9343.
37. Tsao, M.-L.; Platz, M. S. J. Am. Chem. Soc. 2003, 125, 12014.
38. (a) Maltsev, A.; Bally, T.; Tsao, M.-L.; Platz, M. S.; Kuhn, A.; Vosswinkel, M.; Wentrup, C. J. Am. Chem. Soc. 2004, 126, 237.
39. 12 and 11 can thus be estimated as 23 kcal/mol.
40. Tönshoff, C.; Bucher, G. Eur. J. Org. Chem. 2004, 269.
41. Poe, R.; Schnapp, K.; Young, M. J. T.; Grayzar, J.; Platz, M. S. J. Am. Chem. Soc. 1992, 114, 5054.
42. (a) Naito, I.; Oku, A.; Otani, N.; Fujiwara, Y.; Tanimoto, Y. J. Chem. Soc., Perkin Trans. 2 1996, 725.
43. (b) Wang, J.-L.; Yuzawa, T.; Nigam, M.; Likhotvorik, I.; Platz, M. S. J. Phys. Chem. A 2001, 105, 3752.
44. Bucher, G.; Nicolaides, A., unpublished results.
45. (a) We cannot rule out formation of 13 from higher excited singlet states of either 1 or 2.
46. + resulted in cleavage of the N-O bond and convergence to a nitrene structure.
47. Karney, W. L.; Borden, W. T. J. Am. Chem. Soc. 1997, 119, 3347.
48. Johnson, W. T. G.; Sullivan, M. B.; Cramer, C. J. Int. J. Quantum Chem. 2001, 85, 492.
49. (a) Pol'shakov, D. A.; Tsentalovich, Yu. P.; Gritsan, N. P. Kinet. Catal. 2001, 42, 601;
50. Pol'shakov, D. A.; Tsentalovich, Yu. P.; Kinetika Kataliz 2001, 42, 664.
51. max = 511, 447, and 411 nm.
52. Havlas, Z.; Kývala, M.; Michl, J. Collect. Czech. Chem. Commun. 2003, 68, 2335.
53. Leyva, E.; Platz, M. S.; Niu, B.; Wirz, J. J. Phys. Chem. 1987, 91, 2293.
54. -1 (Hadel, L. M.; Platz, M. S.; Scaiano, J. C. J. Am. Chem. Soc. 1984, 106, 283.)
55. 12 by diethylamine also partially accounts for our failure to isolate 5 upon photolysis of complexes of 1 in the presence of diethylamine (Stern-Volmer quenching). In addition, complexes of 5 may also simply be too unstable for isolation (cf. ref 17 and references therein).
56. Foresman, J. B.; Keith, T. A.; Wiberg, K. B.; Snoonian, J.; Frisch, M. J. J. Phys. Chem. 1996, 100, 16098.