Enantioselective Construction of Bridgehead Quaternary Carbon Containing Bicyclo[3.3.1]nonanes by Palladium-Catalyzed ­Desymmetric Arylation

Abstract

An enantioselective and catalytic method for the synthesis of bridgehead quaternary carbon containing bicyclo[3.3.1]nonanes is described. The intramolecular desymmetric arylation of α-disubstituted 1,3-diketones was achieved using a chiral Pd/PHOX complex. A variety of bridged cyclic molecules, common skeleton for polyprenylated acylphloroglucinols, were obtained in up to 84% yield with 86% ee.

Key words

asymmetric catalysis - desymmetrization - all-carbon ­quaternary center - palladium - arylation - bicyclic compound

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