On the Configurational Stability and Reactivity of Tertiary Silyloxy Carbanions Derived from Stereoselective Brook Rearrangement

Here we report a stereospecific Brook rearrangement/trapping sequence, initiated by the formation of a zinc alkoxide from an enantioenriched (hydroxyallyl)silane. The chiral carbanion resulting from the Brook rearrangement is trapped intermolecularly by carbonyl electrophiles with complete transfer of chirality. A concerted mechanism is proposed to rationalize the stereospecificity observed in the reaction sequence.