The Construction of All-Carbon Quaternary Stereocenters by Use of Pd-Catalyzed Asymmetric Allylic Alkylation Reactions in Total Synthesis

All‐carbon quaternary stereocenters have posed significant challenges in the synthesis of complex natural products. These important structural motifs have inspired the development of broadly applicable palladium‐catalyzed asymmetric allylic alkylation reactions of unstabilized non‐biased enolates for the synthesis of enantioenriched α‐quaternary products. This microreview outlines key considerations in the application of palladium‐catalyzed asymmetric allylic alkylation reactions and presents recent total syntheses of complex natural products that have employed these powerful transformations for the direct, catalytic, enantioselective construction of all‐carbon quaternary stereocenters. Pd‐catalyzed asymmetric allylic alkylation reactions are powerful transformations for the direct construction of all‐carbon quaternary stereocenters. A variety of chiral building blocks can be prepared by this approach and these key intermediates have enabled the enantioselective synthesis of complex natural products. Recent advances in reaction methodology and total synthesis are discussed.