학술논문

Recent Advances in Enantioselective Pd-Catalyzed Allylic Substitution: From Design to Applications
Document Type
Source
Chemical Reviews. 121(8):4373-4505
Subject
Allylation
Catalysis
Enantioselectivity
Nucleophiles
Stereochemistry
Substitution reactions
Synthesis (chemical)
Allylic substitution
Carbon nucleophiles
Chronological order
Complex molecules
Enantioselective
Heteronucleophiles
High selectivity
Mechanistic aspects
Ligands
Language
English
ISSN
0009-2665
1520-6890
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. © 2021 American Chemical Society.