Stereoselective synthesis of cis- or trans-3,5-disubstituted pyrazolidines via pd-catalyzed carboamination reactions: Use of allylic strain to control product stereochemistry through N-substituent manipulation

Journal of the American Chemical Society

Volumn 130, Issue 39, 2008, Pages 12907-12911

  Giampietro, Natalie C ^a   Wolfe, John P ^a  

^a UNIVERSITY OF MICHIGAN   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

ALLYLIC STRAIN; BOND CLEAVAGES; DIASTEREO-SELECTIVITY; GOOD YIELD; PYRAZOLINES; SIMPLE MODIFICATIONS; STEREOCONTROL; STEREOSELECTIVE SYNTHESIS; TRANSITION STATE;

AMINES; PALLADIUM; STEREOCHEMISTRY;

STEREOSELECTIVITY;

ALLYL COMPOUND; HYDRAZINE DERIVATIVE; PALLADIUM; PYRAZOLE DERIVATIVE;

AMINATION; ARTICLE; CATALYSIS; CHEMISTRY; STEREOISOMERISM; SYNTHESIS;

ALLYL COMPOUNDS; AMINATION; CATALYSIS; HYDRAZINES; PALLADIUM; PYRAZOLES; STEREOISOMERISM;

EID: 58149173444     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja8050487     Document Type: Article

References (18)

1. For a recent review, see: (a) Wolfe, J. P. Eur. J. Org. Chem. 2007, 571.
2. (a) Wolfe, J. P.; Rossi, M. A. J. Am. Chem. Soc. 2004, 126, 1620. (b) Hay, M. B.; Hardin, A. R.; Wolfe, J. P. J. Org. Chem. 2005, 70, 3099. (c) Ney, J. E.; Wolfe, J. P. Angew. Chem., Int. Ed. 2004, 43, 3605. (d) Bertrand, M. B.; Wolfe, J. P. Tetrahedron 2005, 61, 6447.
3. (a) Hoffmann, R. W. Chem. Rev. 1989, 89, 1841. (b) Maloney, D. J.; Danishefsky, S. J. Angew. Chem., Int. Ed. 2007, 46, 7789.
4. (a) Burgess, L. E.; Meyers, A. I. J. Am. Chem. Soc. 1991, 113, 9858. (b) Giese, B.; Bulliard, M.; Zeitz, H.-G. Synlett 1991, 425. (c) Garcia, E.; Arrasate, S.; Lete, E.; Sotomayor, N. J. Org. Chem. 2005, 70, 10368.
5. For selected syntheses of 3,5-disubstituted or -trisubstituted pyrazolidines, see: (a) Yang, Q.; Jiang, X.; Ma, S. Chem. - Eur. J. 2007, 13, 9310. (b) de los Santos, J. M.; Lopez, Y.; Aparico, D.; Palacios, F. J. Org. Chem. 2008, 73, 550. (c) Yamashita, Y.; Kobayashi, S. J. Am. Chem. Soc. 2004, 126, 11279. (d) Shirakawa, S.; Lombardi, P. J.; Leighton, J. L. J. Am. Chem. Soc. 2005, 127, 9974. (e) Chauveau, A.; Martens, T.; Bonin, M.; Micouin, L.; Husson, H.-P. Synthesis 2002, 1885. (f) Guerra, F. M.; Mish, M. R.; Carreira, E. M. Org. Lett. 2000, 2, 4265.
6. For examples of biologically active pyrazolidines, see: (a) Witherington, J.; Bordas, V.; Gaiba, A.; Green, P. M.; Naylor, A.; Parr, N.; Smith, D. G.; Takle, A. K.; Ward, R. W. Bioorg. Med. Chem. Lett. 2006, 16, 2256. (b) Ahn, J. H.; Kim, J. A.; Kim, H.-M.; Kwon, H.-M.; Huh, S.-C.; Rhee, S. D.; Kim, K. R.; Yang, S.-D.; Park, S.-D.; Lee, J. M.; Kim, S. S.; Cheon, H. G. Bioorg. Med. Chem. Lett. 2005, 15, 1337. (c) Wilkinson, D. E. Bioorg. Med. Chem. 2003, 11, 4815.
7. For examples of biologically active pyrazolines, see: (a) Johnson, M.; Younglove, B.; Lee, L.; LeBlanc, R.; Holt, H., Jr.; Hills, P.; Mackay, H.; Brown, T.; Mooberry, S. L.; Lee, M. Bioorg. Med. Chem. Lett. 2007, 17, 5897. (b) Ali, M. A.; Shaharyar, M. Bioorg. Med. Chem. 2007, 15, 1896. (c) Lange, J. H. M.; Kruse, C. G. Curr. Opin. Drug. Discovery Dev. 2004, 7, 498.
8. For recent synthetic approaches to pyrazolines, see: (a) Alex, K.; Tillack, A.; Schwarz, N.; Beller, M. Org. Lett. 2008, 10, 2377. (b) Nair, V.; Biju, A. T.; Mohanan, K.; Suresh, E. Org. Lett. 2006, 8, 2213. (c) Reference 5b, 5e, and references cited therein.
9. For a recent review on biologically active pyrazoles, see: (a) Elguero, J.; Goya, P.; Jagerovic, N.; Silva, A. M. S. In Targets in Heterocyclic Systems Volume 6; Attanasi, O. A., Spinelli, D. Eds.; Springer: Berlin, 2003; p 52.
10. For recent synthetic approaches to pyrazoles, see: 5. (a) Martin, R.; Rivero, M. R.; Buchwald, S. L. Angew. Chem., Int. Ed. 2006, 45, 7079. (b) Ahmed, M. S.; Kobayashi, K.; Mori, A. Org. Lett. 2005, 7, 4487. (c) Yet, L. Prog. Heterocycl. Chem. 2005, 17, 172-196. (d) Reference 7a and references cited therein.
11. Dppe = 1,2-bis(diphenylphosphino)ethane. Dpe-phos = bis(2- diphenylphosphino)phenyl ether.
12. Use of dppe as ligand provided only trace amounts of pyrazolidine products, and afforded significant amounts of products resulting from Heck-arylation of the starting material.
13. 2 precatalysts provided similar results in these reactions.
14. Fritz, J. A.; Wolfe, J. P. Tetrahedron 2008, 64, 6838.
15. 2-atom. This would decrease the allylic strain interaction present in transition state 1 (Scheme 2) and result in the formation of increased amounts of the minor stereoisomer.
16. It is not clear if the oxidation to the pyrazoline product is Pd-catalyzed or if oxidation occurs upon workup. Air-oxidation of NH-pyrazolidines that lack electron-withdrawing substituents on the second nitrogen atom appears to be very facile.
17. 2-atoms, which leads to greater differences in energy between transition states 1 and 2 (Scheme 2).
18. Ding, H.; Friestad, G. K. Org. Lett. 2004, 6, 637.