Enantioselective Tertiary Electrophile (Hetero)Benzylation: Pd‐Catalyzed Substitution of Isoprene Monoxide with Arylacetates**

The enantioselective generation of quaternary carbon centers remains challenging but is of growing importance for the preparation of functional molecules. Metal catalyzed allylic alkylations of tertiary electrophiles can provide access to these substructures but remain generally incompatible with organometallic benzyl nucleophiles. Here we demonstrate that electron-deficient arylacetates can serve as benzyl nucleophile surrogates to generate enantioenriched acyclic molecules containing a quaternary carbon center via a two-step substitution-decarboxylation process using isoprene monoxide. Products are often obtained in >90 % ee using a commercially available catalyst. An array of electron-withdrawing functional groups on the arylacetate moiety are tolerated. The lactone generated by the initial substitution reaction can be used in further stereoselective transformations to prepare molecules with acyclic vicinal quaternary stereocenters.