Mechanistic studies of copper-catalyzed alkene aziridination

Journal of the American Chemical Society

Volumn 122, Issue 33, 2000, Pages 8013-8020

  Brandt, Peter ^a,c   Södergren, Mikael J ^b   Andersson, Pher G ^b   Norrby, Per Ola ^a  

^a UNIVERSITY OF COPENHAGEN   (Denmark)

^b UPPSALA UNIVERSITY   (Sweden)

^c Karo Bio   (Sweden)

Author keywords

[No Author keywords available]

Indexed keywords

ALKENE; AZIRIDINE DERIVATIVE; COPPER;

ARTICLE; CATALYSIS; CHEMICAL BINDING; CHEMICAL MODIFICATION; CHEMICAL REACTION KINETICS; ENERGY; EPOXIDATION;

EID: 0040518632     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja993246g     Document Type: Article

References (36)

1. Kolb. H. C.; Sharpless, K. B. Asymmetric Dihydroxylation. In Transition Metals for Organic Synthesis; Beller, M., Bolm, C., Eds.; Wiley-VCH: Weinheim. Germany, 1998; pp 219-242.
2. Kolb, H. C.; Sharpless, K. B. Asymmetric Aminohydroxylation. In Transition Metals for Organic Synthesis; Beller, M., Bolm, C., Eds.; Wiley-VCH: Weinheim, Germany, 1998; pp 243-260.
3. Jacobsen, E. N. Asymmetric Catalytic Epoxidation of Unfunctionalized Olefins. In Catalytic Asymmetric Synthesis; Ojima, I., Ed.; VCH Publishers: New York, 1993; pp 159-202.
4. Müller, P. Transition Metal-Catalyzed Nitrene Transfer. In Advances in Catalytic Processes; JAI Press Inc.: Greenwich, CN, 1997; Vol. 2, pp 113-151.
5. Tanner, D. Angew. Chem., Int. Ed. Engl. 1994, 33, 599.
6. Alonso, D. A.; Andersson, P. G. J. Org. Chem. 1998, 63, 9455.
7. (a) Södergren, M. J.; Alonso, D. A.; Bedekar, A. V.; Andersson, P. G. Tetrahedron Lett. 1997, 38, 6897.
8. (b) Södergren, M. J.; Alonso, D. A.; Andersson, P. G. Tetrahedron: Asymmetry 1997, 8, 3563.
9. (c) Dauban, P.; Dodd, R. H. J. Org. Chem. 1999, 64, 5304.
10. Manganese: (a) Noda, K.; Hosoya, N.; Irie, R.; Ito, Y.; Katsuki, T. Synlett 1993, 469. (b) Nishikori, H.; Katsuki, T. Tetrahedron Lett. 1996, 37, 9245. Lai, T.-S.; Kwong, H.-L.; Che, C.-M.; Peng, S.-M. Chem. Commun. 1997, 2373. Ruthenium: (d) Au, S.-M.; Fung, W.-H.; Cheng, M.-C.; Che, C.-M.; Peng, S.-M. Chem. Commun. 1997, 1655. Rhodium: (e) Müller, P.; Baud, C.; Jacquier, Y. Can. J. Chem. 1998, 76, 738.
11. Manganese: (a) Noda, K.; Hosoya, N.; Irie, R.; Ito, Y.; Katsuki, T. Synlett 1993, 469. (b) Nishikori, H.; Katsuki, T. Tetrahedron Lett. 1996, 37, 9245. Lai, T.-S.; Kwong, H.-L.; Che, C.-M.; Peng, S.-M. Chem. Commun. 1997, 2373. Ruthenium: (d) Au, S.-M.; Fung, W.-H.; Cheng, M.-C.; Che, C.-M.; Peng, S.-M. Chem. Commun. 1997, 1655. Rhodium: (e) Müller, P.; Baud, C.; Jacquier, Y. Can. J. Chem. 1998, 76, 738.
12. Manganese: (a) Noda, K.; Hosoya, N.; Irie, R.; Ito, Y.; Katsuki, T. Synlett 1993, 469. (b) Nishikori, H.; Katsuki, T. Tetrahedron Lett. 1996, 37, 9245. Lai, T.-S.; Kwong, H.-L.; Che, C.-M.; Peng, S.-M. Chem. Commun. 1997, 2373. Ruthenium: (d) Au, S.-M.; Fung, W.-H.; Cheng, M.-C.; Che, C.-M.; Peng, S.-M. Chem. Commun. 1997, 1655. Rhodium: (e) Müller, P.; Baud, C.; Jacquier, Y. Can. J. Chem. 1998, 76, 738.
13. Manganese: (a) Noda, K.; Hosoya, N.; Irie, R.; Ito, Y.; Katsuki, T. Synlett 1993, 469. (b) Nishikori, H.; Katsuki, T. Tetrahedron Lett. 1996, 37, 9245. Lai, T.-S.; Kwong, H.-L.; Che, C.-M.; Peng, S.-M. Chem. Commun. 1997, 2373. Ruthenium: (d) Au, S.-M.; Fung, W.-H.; Cheng, M.-C.; Che, C.-M.; Peng, S.-M. Chem. Commun. 1997, 1655. Rhodium: (e) Müller, P.; Baud, C.; Jacquier, Y. Can. J. Chem. 1998, 76, 738.
14. Manganese: (a) Noda, K.; Hosoya, N.; Irie, R.; Ito, Y.; Katsuki, T. Synlett 1993, 469. (b) Nishikori, H.; Katsuki, T. Tetrahedron Lett. 1996, 37, 9245. Lai, T.-S.; Kwong, H.-L.; Che, C.-M.; Peng, S.-M. Chem. Commun. 1997, 2373. Ruthenium: (d) Au, S.-M.; Fung, W.-H.; Cheng, M.-C.; Che, C.-M.; Peng, S.-M. Chem. Commun. 1997, 1655. Rhodium: (e) Müller, P.; Baud, C.; Jacquier, Y. Can. J. Chem. 1998, 76, 738.
15. (a) Evans, D. A.; Faul, M. M.; Bilodeau, M. T. J. Org. Chem. 1991, 56, 6744.
16. (b) Evans, D. A.; Faul, M. M.; Bilodeau, M. T., Anderson, B. A.; Barnes, D. M. J. Am. Chem. Soc. 1993, 115, 5328.
17. Evans, D. A.; Faul, M. M.; Bilodeau, M. T. J. Am. Chem. Soc. 1994, 116, 2742.
18. Li, Z.; Conser, K. R.; Jacobsen, E. J. J. Am. Chem. Soc. 1993, 115, 5326.
19. Li, Z.; Quan, R. W.; Jacobsen, E. J. J. Am. Chem. Soc. 1995, 117, 5889.
20. Díaz-Requejo, M. M.; Pérez, P. J.; Brookhart, M.; Tempelton, J. L. Organometallics 1997, 16, 4399.
21. Linde, C.; Arnold, M.; Norrby, P.-O.; Åkermark, B. Angew Chem. Int. Ed. Engl. 1997, 36, 1802-1803.
22. Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Scuseria, G. E.; Robb, M. A.; Cheeseman, J. R.; Zakrzewski, V. G.; Montgomery, J. A.; Stratmann, R. E., Jr.; 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.; 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.3; Gaussian, Inc.: Pittsburgh, PA, 1998.
23. (a) Becke, A. D. J. Chem. Phys. 1993, 98, 5648-5652.
24. (b) Lee, C.; Yang, W.; Parr, R. G. Phys. Rev. B 1988, 37, 785-789.
25. Hay; P. J.; Wadt, W. R. J. Chem. Phys. 1985, 82, 299.
26. Andrae, D.: Häussermann, U.; Dolg, M.; Stoll, H; Preuss, H. Theor. Chim. Acta 1990, 77, 123.
27. For a similar determination, see Ehlers, E. W.; Böhme, M.; Dapprich, S.; Gobbi, A.; Höllwarth, A.; Jonas, V.; Köhler, K. F.; Stegmann, R.; Veldkamp, A.; Frenking, G. Chem. Phys. Lett. 1993, 208, 111.
28. Quan, R. W.; Li, Z.; Jacobsen, E. J. J. Am. Chem. Soc: 1996, 118, 8156.
29. The quality of PhINTs proved to have a significant influence on the reaction. Reproducible rates and full alkene conversions were more securely obtained using PhINTs prepared by the modified version of the Yamada protocol (see Experimental Section and ref 23).
30. Due to the exothermic nature of the aziridination reaction, the addition PhINTs was added in portions. A simple setup that we found useful for the portionwise, yet quick addition of solids under inert atmosphere is described as follows: Onto the reaction vessel is mounted a Schlenck-type assembly having a female joint with the inlet in parallel with the surface of the reaction medium. In this joint is fixed a rubber septum with a hole of appropriate size to provide a gaslight tit around the body of an open-front, 1 mL plastic syringe (i.e., cut off near the position of the 0 mL mark) containing PhINTs. The apparatus is flushed with argon and the PhINTs addition may in this way be efficiently controlled. The internal temperature is monitored via a thermocouple probe, and by vigorous stirring, the temperature could easily be kept between +0.5 and 1.5 °C, variations, which were found not to interfere with the results at this level of precision.
31. Yamada, Y.; Yamamoto, T.; Okawara, M. Chem. Lett. 1975, 361.
32. The entropic contribution to the free energy of dissociation is around 6-8 kcal/mol. The solvation cannot be reliably estimated for a metal-containing species by any methods available to us, but the increase in surface area and coordination of a solvent molecule to Cu will definitely provide several kcal/mol of stabilization.
33. No monodentate nitrenes were ever located in this study.
34. Días-Requejo, M. M.; Belderrain, T. R.; Nicasio, M. C.; Prieto, F.; Pérez, P. J. Organometallics 1999, 18, 2601.
35. Zhang, W.; Lee, N. H.; Jacobsen, E. N. J. Am. Chem. Soc. 1994, 116, 425.
36. Linde, C.; Åkermark, B.; Norrby, P.-O.; Svensson, M. J. Am. Chem. Soc. 1999, 121, 5083-5084.