Stereoselective synthesis via palladium-catalyzed intramolecular bis-silylation

Stereoselective intramolecular bis-silylation reactions catalyzed by isonitrile-palladium(0) complexes are described. Their useful synthetic applications were demonstrated by stereoselective asymmetric synthesis of a natural product and building blocks, e.g., (-)-avenaciolide was synthesized from (R)-3-vinyl-1-undecen-4-ol, and highly enantio-enriched allylsilanes and allenylsilanes were synthesized from the corresponding optically active allylic and propargylic alcohols, respectively. Attempts at catalytic intramolecular asymmetric bis-silylation with optically active t-alkyl isocyanide complexes are also described.