Enantiomerically pure α-alkylidene β-amino esters from asymmetric addition of metal dienolates to N-sulfinylimines

Journal of Organic Chemistry

Volumn 63, Issue 21, 1998, Pages 7157-7161

  Garcia Ruano J L ^a   Fernandez I ^b   Del Prado Catalina, M ^a   Hermoso, J A ^c   Sanz Aparicio, J ^c   Martinez Ripoll M ^c  

^a UNIVERSIDAD AUTÓNOMA DE MADRID   (Spain)

^b UNIVERSITY OF SEVILLE   (Spain)

^c INSTITUTO DE QUÍMICA FÍSICA ROCASOLANO   (Spain)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 0000804599     PISSN: 00223263     EISSN: None     Source Type: Journal    
DOI: 10.1021/jo972303q     Document Type: Article

References (22)

1. (a) Hua, D. H.; Lagneau, N.; Wang, H.; Chen, J. S. Tetrahedron: Asymmetry 1995, 6, 394 (and references therein).
2. (b) Oppolzer, W.; Froelich, O.; Wiaux-Zamar, C.; Bernardinelli, G. Tetrahedron Lett. 1997, 38, 2825.
3. (c) Viso, A.; Fernández de la Pradilla, R.; Guerrero-Strachan, C.; Alonso, M.; Martínez-Ripoll, M.; André, I. J. Org. Chem. 1997, 62, 2316.
4. (d) Balasubramanian, T.; Hassner, A. Tetrahedron Lett. 1996, 37, 5755.
5. (a) García-Ruano, J. L.; Fernández, I.; del Prado-Catalina, M.; Alcudia-Cruz, A. Tetrahedron: Asymmetry 1996, 7, 3407.
6. (b) García-Ruano, J. L.; Fernández, I.; Hamdouchi, C. Tetrahedron Lett. 1995, 36, 295.
7. Davis, F. A.; Reddy, R. E.; Szewczyk, J. M.; Reddy, G. V.; Portonovo, P. S.; Zhang, H.; Fanelli, D.; Reddy, R. T.; Zhou, P.; Carroll, P. J. J. Org. Chem. 1997, 62, 2555 (and references therein).
8. (a) Davis, F. A.; Reddy, R. T.; Reddy, R. E. J. Org. Chem. 1992, 57, 6387.
9. (b) Davis, F. A.; Reddy, R. E.; Szewczyk, J. M. J. Org. Chem. 1995, 60, 7037.
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11. (d) Fujisawa, T.; Kooriyama, Y.; Shimizu, M. Tetrahedron Lett. 1996, 37, 3881.
12. In this sense, we studied the reaction of the lithium enolate of ethyl butyrate with compound 1 at -78 °C. The formation of a mixture containing significant amounts of four different diastereomers was established from the proton NMR spectra of the reaction crude. Only one of them could be easily separated by flash chromatography, but its configurational assignment was not made.
13. 3.
14. For leading references on the addition of dienolates to carbonyl compounds see, for example: (a) Bellassoued, M.; Habbachi, F.; Gaudemar, M. Tetrahedron 1987, 43, 1785.
15. (b) Bellassoued, M.; Habbachi, F.; Gaudemar, M. Tetrahedron 1985, 41, 1299.
16. (c) Johnson, P. R.; White, J. D. J. Org. Chem. 1984, 49, 4424.
17. (d) Dugger, R. W.; Heatchcock, C. H. J. Org. Chem. 1980, 45, 1181.
18. El Borgi, A.; Bellassoued, M.; Moreau, J. L. C. R. Acad. Sci. II 1988, 307, 1805.
19. van Maanen, H. L.; Kleijn, H.; Jastrzebski, J. T. B. H.; Lakin, M. T.; Spek, A. L.; van Koten, G. J. Org. Chem. 1994, 59, 7839.
20. Davis, F. A.; Zhou, P.; Liang, C.-H.; Reddy, R. E. Tetrahedron: Asymmetry 1995, 6, 1511.
21. 1 would be even more favored because the E-Z equilibrium of the starting dienolate must be shifted to the Z form, as in other stabilized conjugated enolates.12 On the other hand, the change of stereoselectivity, from anti to syn, observed in the addition of dienolate to the sulfinylimine 2 can be explained by considering the higher steric volume of the naphthyl group compared with the p-tolyl group, together with the possible competition between the sulfinylic oxygen and the OMe group for metal chelation.
22. Ireland, R. E.; Willard, A. K. Tetrahedron Lett. 1975, 3975.