Abstract
A procedure for the stereoselective synthesis of substituted alkenes from α-silyl aldehydes, via the Peterson reaction, is described. The protocol for the preparation of α-silyl aldehydes is also included. Organometallic addition to the α-silyl aldehyde gives erythro-β-hydroxysilanes in high yields (85–90%), which undergo elimination on treatment with potassium hydride (KH) or boron trifluoride to afford respectively Z- o E-alkenes (87–90%). The method described has been carried out using α-silyl aldehydes bearing the tert-butyldiphenylsilyl group. This bulky group increases the stability of the silyl aldehyde, enhances the stereoselectivity of the formation of the β-hydroxysilanes and favors the stereocontrol of the elimination step, thus providing high yields of stereo-defined alkenes. Here we describe a two-step protocol for the synthesis of Z-1-phenyl-1-hexene from 2-tert-butyldiphenylsilyl-2-phenylethanal and n-butyllithium, followed by elimination of the resulting (1S*,2R*)-1-tert-butyldiphenylsilyl-1-phenylhexan-2-ol with KH. The total time for the synthesis, purification and isolation of the alkene is 2 days.
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References
Colvin, E.W. Silicon Reagents in Organic Synthesis (Academic Press, London, 1988).
Birkefer, I. & Stuhl, O. in The Chemistry of Organic Silicon Compounds (eds. Patai, S. & Rappoport, Z.) 663–676 (Wiley, Chichester, UK, 1989).
Fleming, I. in Comprehensive Organic Synthesis Vol. 2 (eds. Trost, B.M. & Fleming, I.) 563–593 (Pergamon, Oxford, UK, 1991).
Davies, A.G. in Comprehensive Organometallic Chemistry II Vol. 2, 217 (Pergamon Press, New York, 1995).
Fleming, I. in Science of Synthesis: Houben–Weyl Methods of Molecular Transformations Vol. 4 (Thieme, Stuttgart Gr., 2001).
Auner, N. & Weis, J. Organosilicon Chemistry (Wiley-VCH, Weinheim Gr, 2003).
Weber, W.P. Silicon Reagents for Organic Synthesis (Springer-Verlag, New York, 1983).
Ager, D.J. The Peterson reaction. Synthesis 384–398 (1984).
Peterson, D.J. A carbonyl olefination reaction using silyl-substituted organometallic compounds. J. Org. Chem. 33, 780–784 (1968).
Carey, F.A. & Court, A.S. Silicon-containing carbanions. I. Synthesis of vinyl thioetheres and vinylphosphonates via silicon-modified organolithium reagents. J. Org. Chem. 37, 939–943 (1972).
Chaunet, D.C. & Chang, J.M. Reactions of α-epoxysilanes with organocopper reagents. A stereoselective route to alkenes. Tetrahedron Lett. 34, 3695–3698 (1993).
Hudrlik, P.F. & Peterson, D. Stereospecific olefin-forming elimination reactions of β-hydroxysilanes. J. Am. Chem. Soc. 97, 1464–1468 (1975).
Barbero, A., Blanco, Y., García, C. & Pulido, F.J. The Peterson olefination using the tert-butyldiphenylsilyl group: stereoselective synthesis of di- and trisubstituted alkenes. Synthesis 1223–1228 (2000).
Tietze, L.F., Neumman, T., Kajino, M. & Pretor, M. Efficient synthesis of branched propargyl- and allylsilanes. Synthesis 1003–1006 (1995).
Enders, D., Bhushan, V. & Lohray, B.B. Efficient enantioselective synthesis of allylsilanes by Wittig olefination of α-silyl aldehydes. Tetrahedron Lett. 34, 5067–5070 (1993).
Hudrlik, P.F. & Kulkarni, A.K. α-Silyl aldehydes: preparation and use as stereoselective vinyl cation equivalents. J. Am. Chem. Soc. 103, 6251–6253 (1981).
Duhamel, L., Gralak, J. & Bouyanzer, A. A new route to α-trialkylsilyl aldehydes. The first isolation of α-trimethylsilyl aldehydes. Chem. Commun. 1763–1765 (1993).
Enders, D. in Asymmetric Synthesis Vol. 3 (ed. Morrison, J.D.) 275 (Academic Press, Orlando, FL, 1984).
Procter, G. Asymmetric Synthesis (Oxford University Press, Oxford, UK, 1996).
Barbero, A., et al. Synthesis of vinylsilanes by silyl-cupration of acetylenes using tert-butyldiphenylsilyl-cuprate reagents. J. Chem. Soc. Perkin Trans. I 1525–1532 (1995).
Acknowledgements
We thank the “Junta de Castilla y León” and the Ministry of Science of Spain for financial support. We also thank the Laboratory of Technical Instrumentation of the University of Valladolid for spectroscopic analyses.
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Pulido, F., Barbero, A. Peterson olefination from α-silyl aldehydes. Nat Protoc 1, 2068–2074 (2006). https://doi.org/10.1038/nprot.2006.321
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DOI: https://doi.org/10.1038/nprot.2006.321
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