2021
DOI: 10.1021/acs.chemrev.0c00736
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Recent Advances in Enantioselective Pd-Catalyzed Allylic Substitution: From Design to Applications

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-cataly… Show more

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Cited by 411 publications
(222 citation statements)
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References 741 publications
(1,399 reference statements)
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“…Recently, much progress has been made in this area, especially with respect to efficient new protocols for the assembly of complex all-carbon quaternary stereocenters. [23][24][25][26] This review will summarize examples of the direct construction of quaternary stereocenters by means of palladium-catalyzed decarboxylative asymmetric allylic alkylation since 2018. Selected recent total synthesis of complex natural products involving DAAA as the key step are also presented.…”
Section: Introductionmentioning
confidence: 99%
“…Recently, much progress has been made in this area, especially with respect to efficient new protocols for the assembly of complex all-carbon quaternary stereocenters. [23][24][25][26] This review will summarize examples of the direct construction of quaternary stereocenters by means of palladium-catalyzed decarboxylative asymmetric allylic alkylation since 2018. Selected recent total synthesis of complex natural products involving DAAA as the key step are also presented.…”
Section: Introductionmentioning
confidence: 99%
“…7,8 While this substitution reaction has been widely studied to determine the scope and mechanism, new substrates or nucleophiles usually require a new ligand screen to nd the optimal catalyst. 4,6,9,10,11 The selectivity in this reaction depends on a complex interplay between steric interactions favoring a certain allyl geometry, dynamic interconversion through exo-endo isomerization of the allyl moiety, and electronic effects whereby the ligand can in uence the regioselectivity of nucleophilic attack. 6,12 The catalytic cycle of this reaction proceeds 6,[13][14][15] through an oxidative addition to form the reactive h 3allyl palladium intermediate, which has been studied by X-ray crystallography.…”
mentioning
confidence: 99%
“…The most common chiral ligands to introduce stereoselectivity in this step are phosphorus and nitrogen based bidentate ligands. 6,16,17 There has been interest in using P,N ligands because they can discriminate between the two terminal allylic carbons based on their electronic differentiation, directing the nucleophile towards the allylic carbons trans to the phosphorus atom. Some common ligands used for this reaction include the PHOX ligands, phosphite-oxazoline ligands, and aminoalkyl-phosphine ligands.…”
mentioning
confidence: 99%
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