Synlett 1989; 1989(1): 1-8
DOI: 10.1055/s-1989-34681
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Metamorphosis of Synthetic Strategies with Allylic Silanes: Tetracoordinated Allylic Silanes into Pentacoordinated Allylic Silicates

Hideki Sakurai*
  • *Department of Chemistry, Faculty of Science, Tohoku University, Aoba-ku, Sendai 980, Japan
Further Information

Publication History

Publication Date:
26 February 2002 (online)

The reactions of pentacoordinated allylic silicates are shown to be remarkably different from their tetracoordinated allylic silane counterparts. Extremely high regio- and stereospecificities in the reaction with carbonyl compounds are demonstrated. 1. Introduction 2. Variation of Regiochemistry of Fluoride-Catalyzed Reactions of Allylic Silanes 3. Pentacoordinated Allylic Silicates. Importance of the Lewis Acidity of the Silicon Center 4. Regiospecific and Highly Stereoselective Allylation of Aldehydes with 2-Alkenyltrifluorosilanes Activated by Fluoride Ion 5. Highly Stereoselective Allylation of Aldehydes with Pentacoordinated Allylic Silicates in Hydroxylic Media. Discrimination Between Linear and α-Branched Alkanals 6. Allylation of α-Hydroxy Ketones with 2-Alkenyltrifluorosilanes and 2-Alkenyltrialkoxysilanes in the Presence of Triethylamine. Extremely High Stereochemical Control via Chelated Bicyclic Transition States 7. Diastereochemical Control in Allylation of α-Oxo Carboxylic Acids by the Allylic Silicate Strategy 8. Conclusion