Regio- and stereospecific cleavage of silyl- and disilylepoxides with lithium diphenylphosphide

Chemistry - A European Journal

Volumn 10, Issue 18, 2004, Pages 4491-4497

  Cuadrado, Purificación ^a   González Nogal, Ana M ^a   Sarmentero, M Angeles ^a  

^a UNIVERSITY OF VALLADOLID   (Spain)

Author keywords

Cleavage reactions; Enols; Epoxysilanes; Phosphaalkenes; Silyl enol ethers

Indexed keywords

LITHIUM COMPOUNDS; METHANOL; ORGANOMETALLICS; SILICON COMPOUNDS; SUBSTITUTION REACTIONS;

METHYLATION; SYNTHONS;

STEREOCHEMISTRY;

ALPHA HYDROXYSILANE; DISILYL EPOXIDE; EPOXIDE; LITHIUM DERIVATIVE; LITHIUM DIPHENYLPHOSPHIDE; PHOSPHONIUM DERIVATIVE; SILANE DERIVATIVE; SILYL EPOXIDE; UNCLASSIFIED DRUG; VINYL DERIVATIVE; VINYLPHOSPHINE OXIDE; VINYLPHOSPHONIUM IODIDE; VINYLSILANE;

ARTICLE; METHYLATION; ORGANIC CHEMISTRY; SILYLATION; STEREOSPECIFICITY; SUBSTITUTION REACTION;

EPOXY COMPOUNDS; LITHIUM COMPOUNDS; METHYLATION; MOLECULAR STRUCTURE; ORGANOPHOSPHORUS COMPOUNDS; STEREOISOMERISM;

EID: 4744370814     PISSN: 09476539     EISSN: None     Source Type: Journal    
DOI: 10.1002/chem.200400239     Document Type: Article

References (20)

1. P. Cuadrado, A.M. González-Nogal, Tetrahedron Lett. 1997, 38, 8117.
2. I. Fleming, T. W. Newton, F. Roessler, J. Chem. Soc. Perkin Trans. 1 1981, 2527.
3. A. Barbero, P. Cuadrado, I. Fleming, A. M. González, F. J. Pulido, A. Sánchez, J. Chem. Soc. Perkin Trans. 1 1995, 1525.
4. I. Fleming, M. Rowly, P. Cuadrado, A. M. González-Nogal, F. J. Pulido, Tetrahedron 1989, 45, 413.
5. A. Barbero, P. Cuadrado, I. Fleming, A. M. González, F. J. Pulido, J. Chem. Soc. Perkin Trans. 1 1991, 2811.
6. P. F. Hudrlik, D. Peterson, Tetrahedron Lett. 1974, 1133.
7. P. F. Hudrlik, D. Peterson, J. Am. Chem. Soc. 1975, 97, 1464.
8. Regiospecific β-opening of a tert-butyldiphenylsilylepoxide was observed by us in its reaction with methyllithium at -25 °C (ref. [3]). Other epoxides having hindered silyl groups also underwent β-opening by nucleophiles: B. H. Lipshutz, C. Lindsley, R. Susfalk, T. Gross, Tetrahedron Lett. 1994, 35, 8999.
9. A. G. Brook, S. A. Fieldhouse, J. Organomet. Chem. 1967, 10, 235.
10. A. G. Brook, G. E. LeGrow, D. M. MacRae, Can. J. Chem. 1967, 45, 239.
11. When we treated the epóxides 1m and 1l with lithium phenylsulphide the intermediate of β-cleavage from the tert-butyldiphenylsilylepoxide 1m underwent exclusively Brook rearrangement to give the corresponding silyl enol ether. On the other hand, the intermediate of the dimethylphenylsilylepoxide 1l experienced only partial Brook rearrangement leading to a mixture of the respective silyl enol ether and α-hydroxysilane (unpublished results).
12. E. Zbiral, in Organophosphorus Reagent in Organic Synthesis (Ed.: J. I. G. Cadogan), Academic Press, New York, 1979, pp. 223-265.
13. a) For review, see: I. Fleming, Chimia 1980, 34, 265-271;
14. b) P. Brownbridge, Synthesis 1983, 1-28, 55-104;
15. b) E. W. Colvin, Silicon in Organic Synthesis, Butterworths, London, 1981;
16. c) W. P. Weber, Silicon Reagents for Organic Synthesis, Springer, Berlin, 1983;
17. d) S. Patai, The Chemistry of Organic Silicon Compounds (Ed.: Z. Rappoport), Wiley, Chichester, 1989.
18. 3SiCl led to cis/trans mixtures of silyl enol ethers: P. F. Hudrlik, R. H. Schwartz, A. K. Kulkarni, Tetrahedron Lett. 1979, 2233.
19. I. Fleming, T. W. Newton, J. Chem. Soc. Perkin Trans. 1 1984, 119.
20. P. Cuadrado, A. M. González-Nogal, A. Sánchez, J. Org. Chem. 2001, 66, 1961.