Expanding the substrate scope for C-H amination reactions: Oxidative cyclization of urea and guanidine derivatives

Organic Letters

Volumn 8, Issue 6, 2006, Pages 1073-1076

  Kim, Mihyong ^a   Mulcahy, John V ^a   Espino, Christine G ^a   Du Bois, J ^a  

^a STANFORD UNIVERSITY   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

DRUG DERIVATIVE; GUANIDINE DERIVATIVE; UREA;

AMINATION; ARTICLE; CATALYSIS; CHEMICAL STRUCTURE; CHEMISTRY; CYCLIZATION; OXIDATION REDUCTION REACTION;

AMINATION; CATALYSIS; CYCLIZATION; GUANIDINES; MOLECULAR STRUCTURE; OXIDATION-REDUCTION; UREA;

EID: 33646438818     PISSN: 15237060     EISSN: None     Source Type: Journal    
DOI: 10.1021/ol052920y     Document Type: Article

References (36)

1. (a) Espino, C. G.; Du Bois, J. In Modern Rhodium-Catalyzed Organic Reactions; Evans, P. A., Ed.; Wiley-VCH: Weinheim, 2005; pp 379-416.
2. (b) Halfen J. A. Curr. Org. Chem. 2005, 9, 657-669.
3. (c) Müller, P.; Fruit, C. Chem. Rev. 2003, 103, 2905-2920.
4. (d) Dauban, P.; Dodd, R. H. Synlett 2003, 1571-1586.
5. (a) Du Bois, J. CHEMTRACTS-Org. Chem. 2005, 18, 1-13.
6. (b) Fiori, K. W.; Fleming, J. J.; Du Bois, J. Angew. Chem., Int. Ed. 2004, 43, 4349-4352.
7. (c) Wehn, P. M.; Lee, J.; Du Bois, J. Org. Lett. 2003, 5, 4823-4826.
8. (d) Espino, C. G.; Wehn, P. M.; Chow, J.; Du Bois, J. J. Am. Chem. Soc. 2001, 123, 6935-6936.
9. (e) Espino, C. G.; Du Bois, J. Angew. Chem., Int. Ed. 2001, 40, 598-600.
10. For recent related studies, see: (a) Lebel, H.; Huard, K.; Lectard, S. J. Am. Chem. Soc. 2005, 127, 14198-14199.
11. (b) Cui, Y.; He, C. Angew. Chem., Int. Ed. 2004, 43, 4210-4212.
12. (c) Fruit, C.; Müller, P. Tetrahedron: Asymmetry 2004, 15, 1019-1026.
13. (d) Liang, J.-L.; Yuan, S.-X.; Huang, J.-S.; Yu, W.-Y.; Che, C.-M. Angew. Chem., Int. Ed. 2002, 41, 3465-3468.
14. Also see: Yu, X.-Q.; Huang, J.-S.; Zhou, X.-G.; Che, C.-M. Org. Lett. 2000, 2, 2233-2236.
15. Espino, C. G.; Fiori, K. W.; Kim, M.; Du Bois, J. J. Am. Chem. Soc. 2004, 126, 15378-15379.
16. 2; see ref 4. This catalyst may be purchased from Aldrich Chemical Co. or conveniently prepared on large scale (40 g) in three steps: Fiori, K. W.; Du Bois, J. Manuscript in preparation.
17. For a general review on vicinal diamine synthesis, see: Lucet, D.; Le Gall, T.; Mioskowski, C.; Angew. Chem., Int. Ed. 1998, 37, 2580-2627.
18. Also, see: (a) Dunn, P. J.; Häner, R.; Rapoport, H. J. Org. Chem. 1990, 55, 5017-5025.
19. (b) Jones, R. C. F.; Schofield, J. J. Chem. Soc., Perkin Trans. 1 1990, 375-383.
20. (a) Shue, H.-J.; Chen, X.; Shih, N.-Y.; Blythin, D. J.; Paliwal, S.; Lin, L.; Gu, D.; Schwerdt, J. H.; Shah, S.; Reichard, G. A.; Piwinski, J. J.; Duffy, R. A.; Lachowicz, J. E.; Coffin, V. L.; Liu, F.; Nomeir, A. A.; Morgan, C. A.; Varty, G. B. Biorg. Med. Chem. Lett. 2005, 15, 3896-3899.
21. (b) Berlinck, R. G. S.; Kossuga, M. H. Nat. Prod. Rep. 2005, 22, 516-550.
22. (c) Brackeen, M. F.; Cowan, D. J.; Stafford, J. A.; Schoenen, F. J.; Veal, J. M.; Domanico, P. L.; Rose, D.; Strickland, A. B.; Verghese, M.; Feldman, P. L. J. Med. Chem. 1995, 38, 4848-4854.
23. (a) Dembitsky, V. M. Russ. J. Bioorg. Chem. 2002, 28, 170-182.
24. (b) Al Mourabit, A.; Potier, P. Eur. J. Org. Chem. 2001, 237-243.
25. The mixture of unidentified products does not appear to contain any derived from C-H functionalization.
26. Espino, C. G. Ph.D. Thesis, Stanford University, Stanford, CA, 2004.
27. 4, the reaction of 5 gives < 10% of the desired product 6. With either catalyst, recovered starting material accounts for the mass balance in these reactions.
28. 4 is prepared in an analogous fashion from 1-phenylcyclohexane carboxylic acid.
29. 2NCO is precedented, see: Lohaus, G. Chem. Ber. 1972, 105, 2791-2799.
30. 2 for Rh-catalyzed intermolecular C-H amination and alkene aziridination; see: ref 4 and Guthikonda, K.; Du Bois, J. J. Am. Chem. Soc. 2002, 124, 13672-13673, respectively.
31. For a preparation of related N-arenesulfonyl imidodithionates, see: Gompper, R.; Hägele, W. Chem. Ber. 1966, 99, 2885-2899.
32. For use of these reagents in guanidine synthesis, see: Bosin, T. R.; Hanson, R. N.; Rodricks, J. V.; Simpson, R. A.; Rapoport, H. J. Org. Chem. 1973, 38, 1591-1600.
33. (a) Saulnier, M. G.; Frennesson, D. B.; Deshpande, M. S.; Hansel, S. B.; Vyas, D. M. Bioorg. Med. Chem. Lett. 1994, 4, 1985-1990.
34. (b) Neidlein, R.; Haussmann, W. Angew. Chem., Int. Ed. Engl. 1965, 4, 521-522.
35. 2 under Rh-catalysis to give ketone products (cyclohexanone). We believe that this undesired reaction is the result of either intramolecular C-H insertion or C-H abstraction at the α-center. See refs 1a and 10 for details.
36. The analogous conditions when employed with Tces-protected imidazolidin-2-ones failed to cleave the N-S bond, thus giving the product as the N-sulfated cyclic urea. Preliminary investigations indicate that strongly acidic conditions (e.g., 6 M HCl) may be needed to liberate the fully deprotected urea product.