Article

 

Nucleophilic Addition of Potassium O–Ethyl Dithiocarbonate to Baylis–Hillman Adducts Using 9–BBN as Catalyst

 

Ilsa Hernández–Ibinarriaga, and Luis D. Miranda^*

 

Instituto de Química, Universidad Nacional Autónoma de México, Circuito Exterior, Ciudad Universitaria, México, D.F. 04510, México. ^*Responsible author.

 

Received May 11, 2009
Accepted June 26, 2009

 

Abstract

An efficient diastereoselective Michael addition of the commercial potassium O–ethyl dithiocarbonate to Baylis–Hillman adducts in the presence of 9–BBN (9–borabicyclo[3.3.1]nonane) as a Lewis acid is reported. 9–BBN both protected the hydroxyl group and activated the carbonyl of the Michael acceptor.

Keywords: Xanthates; Baylis–Hillman adducts; 9–BBN as a Lewis acid.

 

Resumen

En este artículo se describe una adición de Michael diastereoselectiva del O–etilditiocarbonato de potasio comercial sobre aductos de Baylis–Hillman, utilizando 9–BBN (9–borabiciclo[3.3.1]no nano) como ácido de Lewis. El 9–BBN protegió el grupo hidroxilo y activó al mismo tiempo el grupo carbonilo del aceptor de Michael.

Keywords: Xantatos; aductos de Baylis–Hillman; 9–BBN, ácido de Lewis.

 

DESCARGAR ARTÍCULO EN FORMATO PDF

 

Acknowledgements

Financial support from the DGAPA–UNAM (project PAPIIT–IN213407) is gratefully acknowledged and Dr. Joseph M. Muchowski for many helpful discussions. Also we thank H. Rios, R. Patiño, J. Pérez, L. Velasco, N. Zavala, E. Hernández, M. I. Chávez and A. Peña for technical support and R. A. Toscano and S. Hernández for X–ray crystallography.

 

References

1. Basavaiah, D.; Rao, A.; Satyanarayana, T. Chem. Rev. 2003, 103, 811–891.         [ Links ]

2. a) Pringle, W.; Sharpless, B.. Tetrahedron Lett. 1999, 40, 5151–5154.         [ Links ] b) Shi, M.; Jiang, J.; Cui, S.; Feng, Y.. J. Chem. Soc., Perkin Trans 1. 2001, 390–393.         [ Links ]

3. a) Basavaiah, D.; Dhrama Rao, P.; Suguna Hyma, R. Tetrahedron. 1996, 52, 8001–8062.         [ Links ] b) Bulliard, M.; Zeitz, H.; Giese, B. Synlett 1991, 423–424.         [ Links ] c) Kamimura, A.; Morita, R.; Matsuura, K.; Omata, Y.; Shirai, M. Tetrahedron Lett. 2002, 43, 6189–6191.         [ Links ]

4. a) Zard, S.Z. Angew. Chem. Int. Ed. Engl. 1997, 36, 672–685.         [ Links ] b) Quiclet–Sire, B.; Zard, S.Z. Chem. Eur. J. 2006, 12, 6002–6016.         [ Links ]

5. Bernard, J.; Favier, A.; Zhang, L.; Nilasaroya, A.; Davis, T.P.; Barner–Kowollik, C.; Stenzel, M.H. Macromolecules. 2005, 38, 5475–5484.         [ Links ]

6. a) Stentiford, R. Synlett. 2000, 1, 159.         [ Links ] b) Bar–Haim, G.; Kol, M. Org. Lett 2004, 6, 3549–3551.         [ Links ] c) Syed, B.M.; Gustafsson, T.; Kihlberg, J. Tetrahedron. 2004, 60, 5571–5575.         [ Links ] d) Gawdzik, B.; Iwanek, W. Tetrahedron Assymm. 2005, 16, 2019–2023.         [ Links ]

7. Crystal structure has been deposited at the Cambridge Crystallographic Data Centre: CCDC (739264). Unit cell parameters: a 6.6820(7) b 7.3796(8) c 23.075(3), alpha 87.113(2) beta 81.463(2) gamma 83.056(2), space group P–1.         [ Links ]

8. Mi, X.; Luo, S.; Cheng, J.–P. J. Org. Chem. 2005, 70, 2338–2341.         [ Links ]

9. Coelho, F.; Almeida, W. P.; Veronese, D.; Mateus, C. R.; Silva Lopes, E. C.; Rossi, R. C.; Silveira, G. P. C.; Pavam, C. H Tetrahedron 2002, 58, 7437–7447.         [ Links ]

10. (a) Sa, M. M.; Ramos, M. D.; Fernandes, L. Tetrahedron 2006, 62, 11652–11656.         [ Links ] (b) Ciganek, E. Organic Reactions (Hoboken, NJ, United States) 1997, pp. 51.         [ Links ]

11. Patil, S. N.; Liu, F. J. Org. Chem. 2007, 72, 6305–6308.         [ Links ]