Synthesis of Biologically Active Natural Products on the Basis of Silafunctional Compounds

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Synthetic methods for stereoselective preparations of polyols have been developed on the basis of silafunctional compounds, of which silicon-carbon bonds can be oxidatively cleaved and hydroxylated. The following results have been obtained.1. Selective alpha-alkylation of (dialkylamino)allylsilanes was achieved by in-situ generation of potassium (dialkylamino)allylsilanes. Total synthesis of ( )-brevicomin was carried out viaseveral steps including the selective alpha-alkylation of (dialkylamino)allylsilane. 2. Selective deoxygenation of (isopropoxy) alpha,beta-epoxy) silanes was found in the reaction with isopropylmagnesium chloride in the presence of CuCN. 3. Stereoselective alpha-hydroxyallylation of aldehydes was achieved by in-situ generation of zinc (dialkylamino)allylsilanes. 4. Selective gamma-allylation of aldehydes was achieved by copper(I) reagents which are in-situ generated by a reaction of CuCN with lithium (dialkylamino)allylsilanes. Usefulness of the gamma-regioselective allylation of aldehydes with (dialkylamino)allylsilanes was demonstrated by synthesis of 2-deoxy-C-nucleoside skeletons.