Simple, Tunable Aziridination Catalysts Based on Poly(pyrazolyl)borate-Copper Complexes

Organic Letters

Volumn 3, Issue 10, 2001, Pages 1423-1425

  Handy, Scott T ^a   Czopp, Mark ^a  

^a BINGHAMTON UNIVERSITY   (United States)

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EID: 0000736455     PISSN: 15237060     EISSN: None     Source Type: Journal    
DOI: 10.1021/ol015539w     Document Type: Article

References (23)

1. For a recent review, see: Small Ring Compounds in Organic Synthesis VI; De Meijere, A., Ed.; Topics in Current Chemistry; Springer-Verlag: Berlin, 2000; Vol. 210.
2. Padwa, A.; Woolhouse, A. D. In Comprehensive Heterocyclic Chemistry: The Structure, Reactions, Synthesis, and Uses of Hetercyclic Compounds; Katritzky, A. R., Rees, C. W., Eds.; Pergamon Press: Oxford, 1984; Vol. 7, p 47. Kemp, J. E. G. In Comprehensive Organic Synthesis; Trost, B. M., Fleming, I., Eds.; Pergamon: Oxford, 1991; Vol. 7, p 469.
3. Padwa, A.; Woolhouse, A. D. In Comprehensive Heterocyclic Chemistry: The Structure, Reactions, Synthesis, and Uses of Hetercyclic Compounds; Katritzky, A. R., Rees, C. W., Eds.; Pergamon Press: Oxford, 1984; Vol. 7, p 47. Kemp, J. E. G. In Comprehensive Organic Synthesis; Trost, B. M., Fleming, I., Eds.; Pergamon: Oxford, 1991; Vol. 7, p 469.
4. For a review of nitrene chemistry, see: Gilchrist, T. E.; Rees, C. W. Carbenes, nitrenes, and arynes; Nelson Press: London, 1969.
5. For examples of catalysts used in aziridinations, see: (Copper) Evans, D. A.; Faul, M. M.; Bilodeau, M. T. J. Am. Chem. Soc. 1994, 116, 2742. Li, Z.; Conser, K. R.; Jacobsen, E. N. J. Am. Chem. Soc. 1993, 115, 5326. Vyas, R.; Chanda, B. M.; Bedekar, A. V. Tetrahedron Lett. 1998, 39, 4715. Ando, T.; Minakata, S.; Ryu, I.; Komatsu, M. Tetrahedron Lett. 1998, 39, 309. (Rhodium) Albone, D. P.; Aujla, P. S.; Taylor, P. C. J. Org. Chem. 1998, 63, 9569. Mueller, P.; Baud, C.; Jacquier, Y. Can. J. Chem. 1998, 76, 738. (Iron and Manganese) Mansuy, D.; Many, J.-P.; Dureault, A.; Bedi, G.; Battieoni, P. J. Chem. Soc., Chem. Commun. 1994, 1161. Simanot, J.- P.; Pecaut, J.; Scheidt, W. R.; Marchon, J.-C. Chem. Commun. 1999, 989. (
6. For examples of catalysts used in aziridinations, see: (Copper) Evans, D. A.; Faul, M. M.; Bilodeau, M. T. J. Am. Chem. Soc. 1994, 116, 2742. Li, Z.; Conser, K. R.; Jacobsen, E. N. J. Am. Chem. Soc. 1993, 115, 5326. Vyas, R.; Chanda, B. M.; Bedekar, A. V. Tetrahedron Lett. 1998, 39, 4715. Ando, T.; Minakata, S.; Ryu, I.; Komatsu, M. Tetrahedron Lett. 1998, 39, 309. (Rhodium) Albone, D. P.; Aujla, P. S.; Taylor, P. C. J. Org. Chem. 1998, 63, 9569. Mueller, P.; Baud, C.; Jacquier, Y. Can. J. Chem. 1998, 76, 738. (Iron and Manganese) Mansuy, D.; Many, J.-P.; Dureault, A.; Bedi, G.; Battieoni, P. J. Chem. Soc., Chem. Commun. 1994, 1161. Simanot, J.- P.; Pecaut, J.; Scheidt, W. R.; Marchon, J.-C. Chem. Commun. 1999, 989. (
7. For examples of catalysts used in aziridinations, see: (Copper) Evans, D. A.; Faul, M. M.; Bilodeau, M. T. J. Am. Chem. Soc. 1994, 116, 2742. Li, Z.; Conser, K. R.; Jacobsen, E. N. J. Am. Chem. Soc. 1993, 115, 5326. Vyas, R.; Chanda, B. M.; Bedekar, A. V. Tetrahedron Lett. 1998, 39, 4715. Ando, T.; Minakata, S.; Ryu, I.; Komatsu, M. Tetrahedron Lett. 1998, 39, 309. (Rhodium) Albone, D. P.; Aujla, P. S.; Taylor, P. C. J. Org. Chem. 1998, 63, 9569. Mueller, P.; Baud, C.; Jacquier, Y. Can. J. Chem. 1998, 76, 738. (Iron and Manganese) Mansuy, D.; Many, J.-P.; Dureault, A.; Bedi, G.; Battieoni, P. J. Chem. Soc., Chem. Commun. 1994, 1161. Simanot, J.- P.; Pecaut, J.; Scheidt, W. R.; Marchon, J.-C. Chem. Commun. 1999, 989. (
8. For examples of catalysts used in aziridinations, see: (Copper) Evans, D. A.; Faul, M. M.; Bilodeau, M. T. J. Am. Chem. Soc. 1994, 116, 2742. Li, Z.; Conser, K. R.; Jacobsen, E. N. J. Am. Chem. Soc. 1993, 115, 5326. Vyas, R.; Chanda, B. M.; Bedekar, A. V. Tetrahedron Lett. 1998, 39, 4715. Ando, T.; Minakata, S.; Ryu, I.; Komatsu, M. Tetrahedron Lett. 1998, 39, 309. (Rhodium) Albone, D. P.; Aujla, P. S.; Taylor, P. C. J. Org. Chem. 1998, 63, 9569. Mueller, P.; Baud, C.; Jacquier, Y. Can. J. Chem. 1998, 76, 738. (Iron and Manganese) Mansuy, D.; Many, J.-P.; Dureault, A.; Bedi, G.; Battieoni, P. J. Chem. Soc., Chem. Commun. 1994, 1161. Simanot, J.- P.; Pecaut, J.; Scheidt, W. R.; Marchon, J.-C. Chem. Commun. 1999, 989. (
9. For examples of catalysts used in aziridinations, see: (Copper) Evans, D. A.; Faul, M. M.; Bilodeau, M. T. J. Am. Chem. Soc. 1994, 116, 2742. Li, Z.; Conser, K. R.; Jacobsen, E. N. J. Am. Chem. Soc. 1993, 115, 5326. Vyas, R.; Chanda, B. M.; Bedekar, A. V. Tetrahedron Lett. 1998, 39, 4715. Ando, T.; Minakata, S.; Ryu, I.; Komatsu, M. Tetrahedron Lett. 1998, 39, 309. (Rhodium) Albone, D. P.; Aujla, P. S.; Taylor, P. C. J. Org. Chem. 1998, 63, 9569. Mueller, P.; Baud, C.; Jacquier, Y. Can. J. Chem. 1998, 76, 738. (Iron and Manganese) Mansuy, D.; Many, J.-P.; Dureault, A.; Bedi, G.; Battieoni, P. J. Chem. Soc., Chem. Commun. 1994, 1161. Simanot, J.- P.; Pecaut, J.; Scheidt, W. R.; Marchon, J.-C. Chem. Commun. 1999, 989. (
10. For examples of catalysts used in aziridinations, see: (Copper) Evans, D. A.; Faul, M. M.; Bilodeau, M. T. J. Am. Chem. Soc. 1994, 116, 2742. Li, Z.; Conser, K. R.; Jacobsen, E. N. J. Am. Chem. Soc. 1993, 115, 5326. Vyas, R.; Chanda, B. M.; Bedekar, A. V. Tetrahedron Lett. 1998, 39, 4715. Ando, T.; Minakata, S.; Ryu, I.; Komatsu, M. Tetrahedron Lett. 1998, 39, 309. (Rhodium) Albone, D. P.; Aujla, P. S.; Taylor, P. C. J. Org. Chem. 1998, 63, 9569. Mueller, P.; Baud, C.; Jacquier, Y. Can. J. Chem. 1998, 76, 738. (Iron and Manganese) Mansuy, D.; Many, J.-P.; Dureault, A.; Bedi, G.; Battieoni, P. J. Chem. Soc., Chem. Commun. 1994, 1161. Simanot, J.- P.; Pecaut, J.; Scheidt, W. R.; Marchon, J.-C. Chem. Commun. 1999, 989. (
11. For examples of catalysts used in aziridinations, see: (Copper) Evans, D. A.; Faul, M. M.; Bilodeau, M. T. J. Am. Chem. Soc. 1994, 116, 2742. Li, Z.; Conser, K. R.; Jacobsen, E. N. J. Am. Chem. Soc. 1993, 115, 5326. Vyas, R.; Chanda, B. M.; Bedekar, A. V. Tetrahedron Lett. 1998, 39, 4715. Ando, T.; Minakata, S.; Ryu, I.; Komatsu, M. Tetrahedron Lett. 1998, 39, 309. (Rhodium) Albone, D. P.; Aujla, P. S.; Taylor, P. C. J. Org. Chem. 1998, 63, 9569. Mueller, P.; Baud, C.; Jacquier, Y. Can. J. Chem. 1998, 76, 738. (Iron and Manganese) Mansuy, D.; Many, J.-P.; Dureault, A.; Bedi, G.; Battieoni, P. J. Chem. Soc., Chem. Commun. 1994, 1161. Simanot, J.- P.; Pecaut, J.; Scheidt, W. R.; Marchon, J.-C. Chem. Commun. 1999, 989. (
12. For examples of catalysts used in aziridinations, see: (Copper) Evans, D. A.; Faul, M. M.; Bilodeau, M. T. J. Am. Chem. Soc. 1994, 116, 2742. Li, Z.; Conser, K. R.; Jacobsen, E. N. J. Am. Chem. Soc. 1993, 115, 5326. Vyas, R.; Chanda, B. M.; Bedekar, A. V. Tetrahedron Lett. 1998, 39, 4715. Ando, T.; Minakata, S.; Ryu, I.; Komatsu, M. Tetrahedron Lett. 1998, 39, 309. (Rhodium) Albone, D. P.; Aujla, P. S.; Taylor, P. C. J. Org. Chem. 1998, 63, 9569. Mueller, P.; Baud, C.; Jacquier, Y. Can. J. Chem. 1998, 76, 738. (Iron and Manganese) Mansuy, D.; Many, J.-P.; Dureault, A.; Bedi, G.; Battieoni, P. J. Chem. Soc., Chem. Commun. 1994, 1161. Simanot, J.-P.; Pecaut, J.; Scheidt, W. R.; Marchon, J.-C. Chem. Commun. 1999, 989. (
13. Halfen, J. A.; Hallman, J. K.; Schultz, J. A.; Emerson, J. P. Organometallics 1999, 18, 5435.
14. For selected mechanistic studies, see: Evans, D. A.; Faul, M. M.; Bilodeau, M. T. J. Am. Chem. Soc. 1994, 116, 2742. Diaz-Requejo, M. M.; Perez, P. J.; Brookhart, M.; Templeton, J. L. Organometallics 1997, 16, 4399.
15. For selected mechanistic studies, see: Evans, D. A.; Faul, M. M.; Bilodeau, M. T. J. Am. Chem. Soc. 1994, 116, 2742. Diaz-Requejo, M. M.; Perez, P. J.; Brookhart, M.; Templeton, J. L. Organometallics 1997, 16, 4399.
16. Mueller, P.; Baud, C.; Jacquier, Y. Can. J. Chem. 1998, 76, 738.
17. Brandt, P.; Soedergren, M. J.; Andersson, P. G.; Norrby, P.-O. J. Am. Chem. Soc. 2000, 122, 8013.
18. Perez, P. J.; Brookhart, M.; Templeton, J. L. Organometallics 1993, 12, 261.
19. For a review of poly(pyrazolyl)borates in general, see: Trofimenko, S. Chem. Rev. 1993, 93, 943.
20. Representative Procedure: To a dry vial under argon was added 2.7 mL of distilled acetonitrile. After argon was bubbled through this solution for 15 min, 8.6 mg (0.027 mmol) of sodium tris(3,5-dimethylpyrazolyl)borate and 2.7 mg (0.027 mmol) of copper(I) chloride were added. The solution was stirred for 5 min, whereupon 0.15 mL (1.34 mmol) of styrene and 100 mg (0.268 mmol) of the iodane were added. The reaction was stirred under argon for 14 h and then quenched by the addition of 3 mL of water. This mixture was extracted with ethyl acetate (3 × 5 mL), dried with magnesium sulfate, and concentrated in vacuo. The crude residue was purified by flash column chromatography (7% ethyl acetate in hexanes as eluent) to afford 56.5 mg (77%) of the aziridine product as a white solid.
21. Trofimenko, S. J. Am. Chem. Soc. 1967, 89, 3170.
22. All compounds displayed spectral properties indistinguishable from those reported in the literature.
23. A possible rational for the enhanced yield in the case of trans-β-methylstyrene using the DP catalyst instead of the TP catalyst would be that the increased steric bulk of the TP catalyst hinders coordination with the olefin, thus increasing nonproductive reaction pathways for the presumed copper-nitrene intermediate. The DP catalyst should be significantly less hindered and thus able to more efficiently coordinate with the olefin and lead to the desired aziridine product. However, in the presence of less hindered olefins (cis or terminal), the less hindered copper-nitrene intermediate with the DP catalyst results in increased nonproductive reaction pathways.