Quaternary Carbon Center Formation by Decarboxylation of Allyl β-Ketoesters

Significance

This is the first example of a Pd-catalyzed decarboxylation of racemic allyl β-ketoesters to form enantioenriched α,α-disubstituted ketones in good to excellent yield and ee. The quaternary carbon stereocenter formation step tolerated a very broad range of functional groups, including alkyl, aryl, and heteroatoms on both cyclic ketoester fragment and allyl moiety. Commercially available t-Bu-phox was optimal for the reaction. This method could provide access to valuable starting materials for natural product synthesis.