Rhodium-Catalyzed Allylic Substitution with an Acyl Anion Equivalent: Stereospecific Construction of Acyclic Quaternary Carbon Stereogenic Centers
2012
Evans, P Andrew | Oliver, Samuel | Chae, Jungha
A highly regio- and stereospecific 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 alkylation reactions. The stereospecific variant of this reaction provides the enantiomerically enriched α-quaternary substituted allylic aryl ketone, which is a particularly challenging intermediate for more conventional enolate-based strategies.
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