New Synthesis of (E)-AllyIsilanes with High Enantiopurity via Diastereoselective Intramolecular Bis-Silylation of Chiral Allylic Alcohols

摘要

Much interest has been focused on the development of new and versatile organosilicon reagents which may be utilized for organic synthesis. Ailylsilanes are one of the convenient organosilicon reagents which have made possible some useful regio- and stereoselective allylations and [3 + 2] cyclizations. Accordingly, the preparation of enantio-enriched allylsilanes is highly desirable. However, widely applicable synthetic methods for their preparation are still limited. It was previously reported by usthat intramolecular bis-silylation of carbon—carbon double bonds was achieved by the use of a palladium(tert-alkyl isocyanide) catalyst. The bis-silylation reaction with various homoallyl alcohols proceeded with high regio- and diastereoselectivities, ultimately leading to the stereoselective synthesis of polyols via oxidative cleavage of the resultant silicon-earbon bonds.