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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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.
The authors declare no competing financial interests.
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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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