Intramolecular additions allylsilanes, stereochemistry

This book chapter is limited to Lewis acid-mediated reactions, and does not discuss the important field of Lewis base-mediated allylations, nor does it describe the reactions of allylsilanes with other electrophiles such as epoxides, imines, and allyl-X (X = -Cl, -OR, -OAc). The SaJcurai reaction has been covered under different forms in reviews focusing on The Stereochemistry of the Sakurai reaction , Intramolecular Addition Reactions of Allylic and Propargylic Silanes ," Selective Reactions Using Allylic Metals , Catalytic Enantioselective Addition of Allylic Organometallic Reagents to Aldehydes and Ketones , and Modem Carbonyl Chemistry . ... 

The whole transformation is an oxidative intramolecular 1,4-addition. Stereochemistry of the 1,4-addition is explained by an intramolecular anti attack of the allylsilane moiety to a Pd(II)-coordinated diene functionality in 26 to generate (jt-allyl)palladium complex 27 followed by an intermolecular anti attack of a chloride ion. The substrate allylsilane is easily prepared by the reaction of the corresponding allylic acetate with PhMCjSiLi. 

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