Rhodium-Catalyzed Allylic Substitution with an Acyl Anion Equivalent: Stereospecific Construction of Acyclic Quaternary Carbon Stereogenic Centers.

A highly regio- and stereospecilic rhodium-catalyzed allylic alkylation of tertiary allylic alcohol derivatives with a cyanohydrin pronucleophile is described. This direct and operationally simple protocol provides a fundamentally novel approach toward the synthesis of α-quaternary substituted ketones and circumvents many of the inherent problems associated with conventional enolate allrylation reactions. The stereospecific variant of this reaction provides the enantiomerically enriched a- quaternary substituted allylic aryl ketone, which is a particularly challenging intermediate for more conventional enolate-based strategies. [ABSTRACT FROM AUTHOR]