title: The Construction of All-Carbon Quaternary Stereocenters by Use of Pd-Catalyzed Asymmetric Allylic Alkylation Reactions in Total Synthesis.
abstract: 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.
authors.affiliation: Warren and Katharine Schlinger Laboratory for Chemistry and Chemical Engineering, Division of Chemistry and Chemical Engineering, California Institute of Technology, 1200 E. California Blvd., MC 101-20, Pasadena, CA 91125, USA, Homepage: http://stoltz.caltech.edu.
authors.forename: Allen Y
authors.initials: AY
authors.lastname: Hong
authors.affiliation: Warren and Katharine Schlinger Laboratory for Chemistry and Chemical Engineering, Division of Chemistry and Chemical Engineering, California Institute of Technology, 1200 E. California Blvd., MC 101-20, Pasadena, CA 91125, USA, Homepage: http://stoltz.caltech.edu.
authors.forename: Brian M
authors.initials: BM
authors.lastname: Stoltz
keywords: All-carbon quaternary stereocenters; Allylation; Asymmetric catalysis; Natural products; Palladium; Total synthesis