Facile synthesis of substituted 5-amino- And 3-amino-1,2,4-thiadiazoles from a common precursor

Organic Letters

Volumn 11, Issue 24, 2009, Pages 5666-5669

  Wehn, Paul M ^a   Harrington, Paul E ^a   Eksterowicz, John E ^a  

^a AMGEN INC   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

BROMINATED HYDROCARBON; PALLADIUM; THIADIAZOLE DERIVATIVE;

ARTICLE; CATALYSIS; CHEMICAL STRUCTURE; CHEMISTRY; COMBINATORIAL CHEMISTRY; SYNTHESIS;

CATALYSIS; COMBINATORIAL CHEMISTRY TECHNIQUES; HYDROCARBONS, BROMINATED; MOLECULAR STRUCTURE; PALLADIUM; THIADIAZOLES;

EID: 72849112604     PISSN: 15237060     EISSN: None     Source Type: Journal    
DOI: 10.1021/ol902371y     Document Type: Article

References (31)

1. Kalgutkar, A. S.; Gardner, I.; Obach, R. S.; Shaffer, C. L.; Callegari, E.; Henne, K. R.; Mutlib, A. E.; Dalvie, D. K.; Lee, J. S.; Nakai, Y.; O'Donnell, J. P.; Boer, J.; Harriman, S. P. Curr. Drug Metab. 2005, 6, 161-225.
2. (a) Sutton, J. C.; Pi, Z.; Ruel, R.; L'Heureux. A.; Thibeault, C.; Lam, P. Y. S. U.S. Patent US20060173002A1, 2006.
3. (b) MacNeil, D. J.; McIntyre, J. H.; van der Ploeg, L. H. T.; Ishihara, A. World Intellectual Property Organization Patent WO04009015A2, 2004.
4. Heitz, S.; Durgeat, M.; Guyot, M. Tetrahedron Lett. 1980, 21, 1457-1458.
5. Wilkins, D. J.; Bradley, P. A. Comprehensive Heterocyclic Chemistry II; Katritzky, A. R., Rees, C. W., Scriven, E. F. V., Eds.; Pergamon: New York, NY, 1996; Vol.4, Chapter 10, pp 307-354.
6. Wu, Y.-J.; Zhang, Y. Tetrahedron Lett. 2008, 49, 2869-2871.
7. Other efficient methods: (a) Martin, D.; Graubaum, H.; Kulpe, S. J. Org. Chem. 1985, 50, 1295-1298.
8. b) Dürüst, Y.; Yildirim, M.; Aycan, A. J. Chem. Res. 2008, 235-239.
9. Bellina, F.; Carpita, A.; Rossi, R. Synthesis 2004, 15, 2419-2440.
10. (a) No yield reported: Krenitsky, P.; Joshi, P.; Wilson, D. M.; Termin, A. P.; Fanning, L. T. D. World Intellectual Property Organization Patent, WO06130493A2, 2006. A patent claiming Suzuki coupling on a related chloride derivative in a single example:
11. (b) Apodaca, R.; Breitenbucher, J. G.; Pattabiraman, K.; Seierstad, M.; Xiao, W. U.S. Patent US20070004741A1, 2007.
12. Prepared on multigram scale by reacting 3-bromo-5-chloro-1,2,4- thiadiazole with, ammonia in EtOH (see Supporting Information).
13. There are few reports of successful Suzuki-Miyaura reactions in the presence of unprotected heteroaryl amines. For leading approaches see the following and references therein: (a) Billingsley, K.; Buchwald, S. L. J. Am. Chem. Soc. 2007, 129, 3358-3366.
14. (b) Guram, A. S.; Wang, X.; Bunel, E. E.; Faul, M. M.; Larsen, R. D.; Martinelli, M. J. J. Org. Chem. 2007, 72, 5104-5112.
15. (c) Kudo, N.; Perseghini, M.; Fu, G. C. Angew. Chem., Int. Ed 2006, 45, 1282-1284.
16. (d) Itoh, T.; Mase, T. Tetrahedron Lett. 2005, 46, 3573-3577.
17. Heating the unprotected 5-amino-3-bromo-1,2,4-thiadiazole in the presence of carbonate base leads to decomposition.
18. Caron, S.; Masset, S. S.; Bogle, D. E.; Castaldi, M. J.; Braish, T. F. Org. Process Res. Dev. 2001, 5, 254-256.
19. 2(D-tBPF). Both catalysts were ineffective when coupling was attempted in the presence of the unprotected amino group.
20. The use of boronic acids or esters reflects availability and not an attempt to optimize yield.
21. 2 with aliphatic boronates has been observed previously, see ref 10b.
22. Schröter, S.; Stock, C.; Bach, T. Tetrahedron 2005, 61, 2245-2267.
23. Such reactivity has been observed before for 3-bromo-5-chloro-1,2,4- thiadiazole. Single example of Stille coupling of a vinyl stannane, see: (a) Dart, M. J.; Searle, X. B.; Tietje, K.; Toupence, R. B. U.S. Patent US20040044029A1, 2004.
24. Single example of Suzuki-Miyaura coupling, see: (b) Sawyer, J. S.; Beight, D. W.; Smith, E. C. R.; McMillen, W. T. U.S. Patent US6797723, 2004.
25. Yield is reduced by formation of small amounts of the bis-coupled product. For non-polar products, the use of 1.75 equiv of thiadiazole minimizes formation of the bis-coupled product that can complicate purification of the mono-coupled product.
26. Buchwald-Hartwig amination: Blurton, P.; Fletcher, S.; Teall, M.; Harrison, T.; Munoz, B.; Rivkin, A.; Hamblett, C.; Siliphaivanh, P.; Otte, K. World Intellectual Property Organization Patent, WO08099210A2, 2008.
27. For a related approach to the synthesis of 3-amino-5-substituted-1,2,4- thiadiazoles see: Reiter, L. A.; Subramanyam, C.; Mangual, E. J.; Jones, C. S.; Smeets, M. I.; Brissette, W. H.; McCurdy, S. P.; Lira, P. D.; Linde, R. G.; Li, Q.; Zhang, F.; Antipas, A. S.; Blumberg, L. C.; Doty, J. L.; Driscoll, J. P.; Munchhof, M. J.; Ripp, S. L.; Shavnya, A.; Shepard, R. M.; Sperger, D.; Thomasco, L. M.; Trevena, K. A.; Wolf-Gouveia, L. A.; Zhang, L. Bioorg. Med. Chem. Lett. 2007, 17, 5447-5454.
28. Mangalagiu, I.; Benneche, T.; Undheim, K. Acta Chem. Scand. 1996, 50, 914-917.
29. Legault, C. Y.; Garcia, Y.; Merlic, C. A.; Houk, K. N. J. Am. Chem. Soc. 2007, 129, 12664-12665.
30. (b) Garcia, Y.; Schoenebeck, F.; Legault, C. Y.; Merlic, C. A.; Houk, K. N. J. Am. Chem, Soc 2009, 131, 6632-6639.
31. The calculated bond dissociation energies for the C-Cl and C-Br bonds are 88.2 and 80.4 kcal/mol, respectively. The bond dissociation energies of the carbon-halogen bonds were calculated using B3LYP/6-31G(d). These results strongly suggest control of chemoselectivity by FMO interactions between the heterocycle and palladium catalyst.