Copper(I)-catalyzed synthesis of azoles. DFT study predicts unprecedented reactivity and intermediates

Journal of the American Chemical Society

Volumn 127, Issue 1, 2005, Pages 210-216

  Himo, Fahmi ^a   Lovell, Timothy ^a   Hilgraf, Robert ^a   Rostovtsev, Vsevolod V ^a   Noodleman, Louis ^a   Sharpless, K Barry ^a   Fokin, Valery V ^a  

^a SCRIPPS RESEARCH INSTITUTE   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

CATALYSIS; CHEMICAL ACTIVATION; COMPUTATIONAL COMPLEXITY;

3,4-DISUBSTITUTED ISOXAZOLES; AZIDES; AZOLES; NITRILE OXIDES;

COPPER;

AZIDE; COPPER ACETYLIDE; COPPER DERIVATIVE; ISOXAZOLE; NITRILE OXIDE; PYRROLE; TRIAZOLE; UNCLASSIFIED DRUG;

ARTICLE; CATALYSIS; CHEMICAL REACTION; CHEMICAL REACTION KINETICS; DENSITY FUNCTIONAL THEORY; SYNTHESIS;

CATALYSIS; CATIONS, MONOVALENT; COPPER; ISOXAZOLES; MODELS, MOLECULAR; NITRILES; THERMODYNAMICS; TRIAZOLES;

EID: 11844255741     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja0471525     Document Type: Article

References (29)

1. (a) Rostovtsev, V. V.; Green, L. G.; Fokin, V. V.; Sharpless, K. B. Angew. Chem., Int. Ed. 2002, 41, 2596.
2. (b) Tornøe, C. W.; Christensen, C.; Meldal, M. J. Org. Chem. 2002, 67, 3057.
3. (a) Kolb, H. C.; Finn, M. G.; Sharpless, K. B. Angew. Chem., Int. Ed. 2001, 40, 2004.
4. (b) Kolb, H. C.; Sharpless, K. B. Drug Discovery Today 2003, 8, 1128.
5. Wang, Q.; Chan, T. R.; Hilgraf, R.; Fokin, V. V.; Sharpless, K. B.; Finn, M. G. J. Am. Chem. Soc. 2003, 125, 3192.
6. (a) Speers, A. E.; Cravatt, B. F. Chem. Biol. 2004, 11, 535.
7. (b) Speers, A. E.; Adam, G. C.; Cravatt, B. F. J. Am. Chem. Soc. 2003, 125, 4686.
8. (a) Link, A. J.; Tirrell, D. A. J. Am. Chem. Soc. 2003, 125, 11164.
9. (b) Deiters, A.; Cropp, T.. A.; Mukherji, M.; Chin, J. W.; Anderson, J. C.; Schultz, P. G. J. Am. Chem. Soc. 2003, 125, 11782-11783.
10. Lee, L. V.; Mitchell, M. L.; Huang, S.-J.; Fokin, V. V.; Sharpless, K. B.; Wong, C.-H. J. Am. Chem. Soc. 2003, 125, 9588.
11. (a) Wu, P.; Feldman, A. K.; Nugent, A. K.; Hawker, C. J.; Scheel, A.; Voit, B.; Pyun, J.; Fréchet, J. M. J.; Sharpless, K. B.; Fokin, V. V. Angew. Chem., Int. Ed. 2004, 43, 3928-3932.
12. (b) Díaz, D. D.; Punna, S.; Holzer, P.; McPherson, A. K.; Sharpless, K. B.; Fokin, V. V.; Finn, M. G. J. Polym. Sci., Part A 2004, 42, 4392-4403.
13. Fokin, V. V., unpublished.
14. (a) Becke, A. D. Phys. Rev. 1988, A38, 3098.
15. (b) Becke, A. D. J. Chem. Phys. 1993, 98, 1372.
16. (c) Becke, A. D. J. Chem. Phys. 1993, 98, 5648.
17. 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.; 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.
18. (a) Barone, V.; Cossi, M. J. Phys. Chem. 1998, 102, 1995.
19. (b) Barone, B.; Cossi, M.; Tomasi, J. J. Comput. Chem. 1998, 19, 404.
20. Orozco, M.; Luque, F. J. Chem. Rev. 2000, 100, 4187.
21. Ciavatta, L.; Fern, D.; Palombari, R. J. Inorg. Nucl. Chem. 1980, 42, 593.
22. (a) Huisgen, R. In 1,3-Dipolar Cycloaddition Chemistry; Padwa, A., Ed.; Wiley: New York, 1984; Vol. 1, pp 1-176.
23. (b) Jäger, V.; Colinas, P. A. In Heterocyclic Compounds; Padwa, A., Pearson, W. H., Eds.; Wiley: New York, 2002; Vol. 59, pp 363-461.
24. (a) Grundaman, C.; Richter, R. J. Org. Chem. 1969, 34, 476.
25. (b) Liu, K.-C.; Shelton, B. R.; Howe, R. K. J. Org. Chem. 1980, 45, 3916.
26. (c) Hallig, K.; Torssell, K. B. G.; Hazell, R. G. Acta Chem. Scand. 1991, 45, 736.
27. The uncatalyzed cycloaddition of nitrile oxides to alkynes displays a barrier of 20.2 kcal/mol (i.e., some 6 kcal/mol lower than for the azides, hence the faster thermal reaction). The copper catalyzed reaction barrier is calculated to be 13.2 kcal/mol, a difference of 7 kcal/mol, that is, almost 5 orders of magnitude faster.
28. Mykhalichko, B. M.; Temkin, O. N.; Mys'kiv, M. G. Russ. Chem. Rev. 2001, 69, 957.
29. 2O.