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Recent Advances in Enantioselective Pd-Catalyzed Allylic Substitution: From Design to Applications

2021/03/19 by Òscar Pàmies, Jèssica Margalef, Santiago Cañellas +8 · 1 citation
Chemistry · #Asymmetric Hydrogenation and Catalysis #Asymmetric Synthesis and Catalysis #Catalytic C–H Functionalization Methods

paper · doi:10.1021/acs.chemrev.0c00736

openalex publication_date 2021/03/19 · openalex created_date 2025/10/10 · openalex updated_date 2026/07/29

Abstract

This Review compiles the evolution, mechanistic understanding, and more recent advances in enantioselective Pd-catalyzed allylic substitution and decarboxylative and oxidative allylic substitutions. For each reaction, the catalytic data, as well as examples of their application to the synthesis of more complex molecules, are collected. Sections in which we discuss key mechanistic aspects for high selectivity and a comparison with other metals (with advantages and disadvantages) are also included. For Pd-catalyzed asymmetric allylic substitution, the catalytic data are grouped according to the type of nucleophile employed. Because of the prominent position of the use of stabilized carbon nucleophiles and heteronucleophiles, many chiral ligands have been developed. To better compare the results, they are presented grouped by ligand types. Pd-catalyzed asymmetric decarboxylative reactions are mainly promoted by PHOX or Trost ligands, which justifies organizing this section in chronological order. For asymmetric oxidative allylic substitution the results are grouped according to the type of nucleophile used.

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