Regiocontrolled Oxidative C—C Coupling of Dienol Ethers and 1,3‐Dicarbonyl Compounds.

A strategy for synthesis of γ-alkylated enones through oxidative coupling of siloxydienes and 1,3-dicarbonyl compounds is reported. This method is an interrupted form of our formal [3 + 2] cycloaddition method reported previously. The present work excels in generating all-carbon quaternary centers via C–C bond formation at the remote γ-site which is traditionally challenging to functionalize. Stereoselectivity and functional group tolerance are examined in complex systems. Double alkylation reactions are also described.