Hydrazides as tunable reagents for alkene hydroamination and aminocarbonylation

Journal of the American Chemical Society

Volumn 131, Issue 25, 2009, Pages 8740-8741

  Roveda, Jean Grégoire ^a   Clavette, Christian ^a   Hunt, Ashley D ^a   Gorelsky, Serge I ^a   Whipp, Christopher J ^a   Beauchemin, André M ^a  

^a UNIVERSITY OF OTTAWA   (Canada)

Author keywords

[No Author keywords available]

Indexed keywords

CHEMICAL EQUATIONS; DFT CALCULATION; HIGH TEMPERATURE; HYDRAZINIUM; HYDROAMINATION; INTRAMOLECULAR HYDROAMINATION; SIMPLE MODIFICATIONS; STEREOSPECIFIC; THERMALLY STABLE;

OLEFINS; PROTON TRANSFER; SULFUR COMPOUNDS;

AMINATION;

ALKENE; HYDRAZIDE DERIVATIVE; REAGENT;

AMINATION; ARTICLE; CARBONYLATION; CHEMICAL REACTION KINETICS; CHROMATOGRAPHY; CYCLIZATION; FOURIER TRANSFORMATION; MOLECULAR INTERACTION; SUBSTITUTION REACTION; TEMPERATURE;

ALKENES; AMINATION; BENZOATES; HEATING; HYDRAZINES; INDICATORS AND REAGENTS; MODELS, MOLECULAR; MOLECULAR STRUCTURE; THERMODYNAMICS;

EID: 67649628231     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja902558j     Document Type: Article

References (31)

1. Duggers, R. W.; Ragan, J. A.; Brown Ripin, D. H. Org. Process Res. Dev. 2005, 9, 253.
2. (b) Carey, J. S.; Laffan, D.; Thomson, C.; Williams, M. T. Org. Biomol. Chem. 2006, 4, 2337.
3. For selected reviews, see: (a) Müller, T. E.; Hultzsch, K. C.; Yus, M.; Foubelo, F.; Tada, M. Chem. Rev. 2008, 108, 3795. and reviews cited therein.
4. (b) Aillaud, I.; Collin, J.; Hannedouche, J.; Schulz, E. Dalton Trans. 2007, 5105.
5. (c) Hultzsch, K. C. Adv. Synth. Catal. 2005, 347, 367.
6. (d) Nobis, M.; Drießen-Hölscher, B. Angew. Chem., Int. Ed. 2001, 40, 3983.
7. (e) Müller, T. E.; Beller, M. Chem. Rev. 1998, 98, 675.
8. For examples of metal-catalyzed hydrohydrazidations, see: (a) Waser, J.; Carreira, E. M. J. Am. Chem. Soc. 2004, 126, 5676.
9. (b) Waser, J.; Carreira, E. M. Angew. Chem., Int. Ed. 2004, 43, 4099.
10. (c) Waser, J.; Gaspar, B.; Nambu, H.; Carreira, E. M. J. Am. Chem. Soc. 2006, 128, 11693.
11. (d) Alex, K.; Tillack, A.; Schwarz, N.; Beller, M. Angew. Chem., Int. Ed. 2008, 47, 2304, and references cited therein.
12. (e) Li, Y.; Shi, Y.; Odom, A. L. J. Am. Chem. Soc. 2004, 126, 1794.
13. (f) Cao, C.; Shi, Y.; Odom, A. L. Org. Lett. 2002, 4, 2853.
14. (a) Beauchemin, A. M.; Moran, J.; Lebrun, M.-E.; Séguin, C.; Dimitrijevic, E.; Zhang, L.; Gorelsky, S. I. Angew. Chem., Int. Ed. 2008, 47, 1410.
15. (b) Moran, J.; Gorelsky, S. I.; Dimitrijevic, E.; Lebrun, M.-E.; Bédard, A.-C.; Séguin, C.; Beauchemin, A. M. J. Am. Chem. Soc. 2008, 130, 17893.
16. (c) Bourgeois, J.; Dion, I.; Cebrowski, P. H.; Loiseau, F.; Bédard, A.-C.; Beauchemin, A. M. J. Am. Chem. Soc. 2009, 131, 874.
17. (d) Moran, J.; Pfeiffer, J. Y.; Gorelsky, S. I.; Beauchemin, A. M. Org. Lett. 2009, 11, 1895.
18. Such reactions are also called reverse Cope cyclizations/eliminations. For a review, see: Cooper, N. J.; Knight, D. W. Tetrahedron 2004, 60, 243.
19. For analogous intermolecular reactivity of hydrazines with alkynes, see: Cebrowski, P. H.; Roveda, J.-G.; Moran, J.; Gorelsky, S. I.; Beauchemin, A. M. Chem. Commun. 2008, 492.
20. For a recent review on methods to access di- and trisubstituted hydrazides, see: Licandro, E.; Perdicchia, D. Eur. J. Org. Chem. 2004, 665.
21. For metal-catalyzed variants, see: (a) Hegedus, L. S.; Allen, G. F.; Olsen, D. J. J. Am. Chem. Soc. 1980, 102, 3583.
22. (b) Hegedus, L. S.; McKearin, J. M. J. Am. Chem. Soc. 1982, 104, 2444.
23. (c) Beccalli, E. D.; Broggini, G.; Martinelli, M.; Sottocornola, S. Chem. Rev. 2007, 107, 5318.
24. (d) Cernak, T. A.; Lambert, T. H. J. Am. Chem. Soc. 2009, 131, 3124.
25. The reaction can also be performed in PhMe, dioxane, MeCN, i-PrOH, DMF, and H2O. See Supporting Information for details.
26. For hydroxylamines, the proton transfer step of the N-oxide intermediate is kinetically relevant, and the increased reactivity observed in protic solvents (e.g., n-PrOH) is consistent with a bimolecular proton transfer process (e.g., n-PrOH-mediated). See refs 4a,b.
27. Formation of product 7g in entry 6 is consistent with epimerization of product 7e. See Supporting Information for details.
28. For precedence on aminoisocyanates formation from similar precursors, see: Wadsworth, W. S.; Emmons, W. D. J. Org. Chem. 1967, 32, 1279.
29. Reports on the reactivity of aminoisocyanates are scarce, and such species are known to dimerize and trimerize. For other reactivity, see: (a) Lockley, W. J. S.; Lwowski, W. Tetrahedron Lett. 1974, 4263.
30. (b) Kurz, M.; Reichen, W. Tetrahedron Lett. 1978, 1433.
31. (c) Reference 12 (and references cited therein).