Carboxylate methylenation with a functionalized silylmethyl anion: A two-step synthesis of 2-substituted allylic alcohols from esters

Journal of Organic Chemistry

Volumn 61, Issue 26, 1996, Pages 9617-9620

  Mickelson, Tammy J ^a,c   Koviach, Jennifer L ^a   Forsyth, Craig J ^a,b  

^a UNIVERSITY OF MINNESOTA   (United States)

^b University of Minnesota   (United States)

^c UNIVERSITY OF ROCHESTER   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 0000538271     PISSN: 00223263     EISSN: None     Source Type: Journal    
DOI: 10.1021/jo961639h     Document Type: Article

References (18)

1. Fleming, I. In Comprehensive Organic Synthesis; Heathcock, C. H., Ed.; Pergamon Press: Oxford, 1991; Vol. 2, pp 595-628.
2. Anderson, M. B.; Fuchs, P. L. Synth. Commun. 1987, 17, 621-635.
3. Narayanan, B. A.; Bunnelle, W. H. Tetrahedron Lett. 1987, 28, 6261-6264.
4. Lee, T. V.; Porter, J. R.; Roden, F. S. Tetrahedron Lett. 1988, 29, 5009-5012.
5. Lee, T. V.; Channon, J. A.; Cregg, C.; Porter, J. R.; Roden, F. S.; Yeoh, H. T.-L. Tetrahedron 1989, 45, 5877-5886.
6. Fleming, I.; Pearce, A. J. Chem. Soc., Perkin Trans. I 1981, 251.
7. Tamao, K.; Ishida, N.; Tanaka, T.; Kumada, M. Organometallics 1983, 2, 1694-1696.
8. Tamao, K.; Kakui, T.; Akita, M.; Iwahara, T.; Kanatani, R. Tetrahedron 1983, 39, 983-990.
9. Demuth, M. Helv. Chim. Acta 1978, 61, 3136.
10. Bunnelle, W. H.; Narayanan, B. A. Org. Synth. 1990, 69, 89-95.
11. Tamao, K.; Ishida, N. Tetrahedron Lett. 1984, 25, 4245-4248.
12. Tamao, K.; Ishida, N.; Ito, Y.; Kumada, M. Org. Synth. 1990, 69, 96-105.
13. Keck, G. E.; Palani, A.; McHardy, S. F. J. Org. Chem. 1994, 59, 3112-3122.
14. Baker, K. V.; Brown, J. M.; Hughe, N.; Skarnulis, A. J.; Sexton, A. J. Org. Chem. 1991, 56, 698-703.
15. Evans, W. J.; Feldman, J. D.; Ziller, J. W. J. Am. Chem. Soc. 1996, 118, 4581-4584.
16. The resultant disiloxanes could be oxidized to the corresponding allylic alcohols under the same conditions as used for 3, but lower yields of allylic alcohol products were obtained.
17. The stability of the isopropyl silyl ether proved useful for demonstrating the utility of this methodology; however, the scope of this chemistry may be expanded by the use of functionalized alkyl groups in place of the isopropyl group of 1. For example, methyl carboxylate methylenation using the reagent derived from (chloromethyl)dimethyl(allyloxy)silane also gave the corresponding allylic silane (data not shown). Such alternatively functionalized silylmethyl anions may lead to allylic silanes suitable for a variety of subsequent intramolecular transformations via this new type of temporary silicon connection.
18. Kirmse, W.; Rode, J. Chem. Ber. 1986, 119, 3694-3703.