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Enantioconvergent catalysis enables the conversion of racemic molecules into a single enantiomer in perfect yield and is considered an ideal approach for asymmetric synthesis. Despite remarkable advances in this field, enantioconvergent transformations of inert tertiary C−H bonds remain largely unexplored due to the high bond dissociation energy and the surrounding steric repulsion that pose unparalleled constraints on bond cleavage and formation. Here, we report an enantioconvergent Pd‐catalyzed alkylation of racemic tertiary allylic C−H bonds of α‐alkenes, providing a unique approach to access a broad range of enantioenriched γ,δ‐unsaturated carbonyl compounds featuring quaternary carbon stereocenters. Mechanistic studies reveal that a stereoablative event occurs through the rate‐limiting cleavage of tertiary allylic C−H bonds to generate σ‐allyl‐Pd species, and the achieved E/Z‐selectivity of σ‐allyl‐Pd species effectively regulates the diastereoselectivity via a nucleophile coordination‐enabled SN2′‐allylation pathway. [ABSTRACT FROM AUTHOR]

Enantioconvergent catalysis enables the conversion of racemic molecules into a single enantiomer in perfect yield and is considered an ideal approach for asymmetric synthesis. Despite remarkable advances in this field, enantioconvergent transformations of inert tertiary C−H bonds remain largely unexplored due to the high bond dissociation energy and the surrounding steric repulsion that pose unparalleled constraints on bond cleavage and formation. Here, we report an enantioconvergent Pd‐catalyzed alkylation of racemic tertiary allylic C−H bonds of α‐alkenes, providing a unique approach to access a broad range of enantioenriched γ,δ‐unsaturated carbonyl compounds featuring quaternary carbon stereocenters. Mechanistic studies reveal that a stereoablative event occurs through the rate‐limiting cleavage of tertiary allylic C−H bonds to generate σ‐allyl‐Pd species, and the achieved E/Z‐selectivity of σ‐allyl‐Pd species effectively regulates the diastereoselectivity via a nucleophile coordination‐enabled SN2′‐allylation pathway. [ABSTRACT FROM AUTHOR]