Palladium-catalyzed decarboxylative allylic alkylation of diastereomeric β-ketoesters

Ma, Sandy; Reeves, Corey M.; Craig, Robert A.; Stoltz, Brian M.

doi:10.1016/j.tet.2014.03.042

Cited by 6 publications

(2 citation statements)

References 10 publications

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“…His group investigated the Pd-catalyzed DAAA of diastereomeric β-ketoesters in 2014 to learn if the process was indeed a stereoablative transformation ( Scheme 247 ). 646 Two diastereomeric substrates (±)- 211 and (±)- 212 with opposite configuration at the α-position were tested in the DAAA. The comparable diastereomeric product ratios (3/1 dr) found for both substrates are highly suggestive of a stereoablative process.…”

Section: Asymmetric Decarboxylative Allylic Substitutionmentioning

confidence: 99%

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

Pàmies

Margalef

Cañellas³

et al. 2021

Chem. Rev.

329

202

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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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Section: Asymmetric Decarboxylative Allylic Substitutionmentioning

confidence: 99%

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

Pàmies

Margalef

Cañellas³

et al. 2021

Chem. Rev.

329

202

View full text Add to dashboard Cite

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“…Substantial effort has resulted in a detailed mechanistic understanding of this stereoablative process. − Preliminary studies (Scheme ) suggested that an internal mechanism (i.e., reductive elimination) is a lower-energy pathway than the corresponding external mechanism involving attack of the enolate onto an η 3 -allyl complex; it was later discovered that η 1 -allylpalladium carboxylate 5 was found to be the resting state of the catalyst and that decarboxylation was likely rate-limiting. − The lowest-energy pathway for carbon–carbon bond formation occurs through a seven-membered, Claisen-like transition state ( 6 ) similar to that originally proposed by Echavarren and co-workers, in which the chiral ligand imparts facial selectivity of the allylic alkylation. The sigmatropic character of the transition state likely accounts for the high efficiency with which these sterically hindered quaternary centers are formed, as sigmatropic rearrangements remain a preeminent method for their construction .…”

Section: Stereoablative Transformationsmentioning

confidence: 99%

Advances in Stereoconvergent Catalysis from 2005 to 2015: Transition-Metal-Mediated Stereoablative Reactions, Dynamic Kinetic Resolutions, and Dynamic Kinetic Asymmetric Transformations

et al. 2017

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An important subset of asymmetric synthesis is dynamic kinetic resolution, dynamic kinetic asymmetric processes and stereoablative transformations. Initially, only enzymes were known to catalyze dynamic kinetic processes but recently various synthetic catalysts have been developed. This review summarizes major advances in non-enzymatic, transition metal promoted dynamic asymmetric transformations reported between 2005 and 2015.

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Palladium‐Catalyzed Decarboxylative Asymmetric Allylic Alkylation: Development, Mechanistic Understanding and Recent Advances

2019

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The palladium‐catalyzed decarboxylative asymmetric allylic alkylation (DAAA) is comprehensively reviewed, from its original development to recent advances in terms of substrate scope, reactivity, regio‐ and enantioselectivity. The current understanding of the mechanistic details, based on a combination of experimental and computational studies, is described. Selected examples of the application of this asymmetric synthetic methodology in natural product synthesis are given. The exploration of Pd‐catalyzed decarboxylative asymmetric catalysis, in particular, the related interceptive decarboxylative asymmetric allylic alkylation, has become a focus in recent years and this is also summarized.

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Palladium-catalyzed decarboxylative allylic alkylation of diastereomeric β-ketoesters

Cited by 6 publications

References 10 publications

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

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

Advances in Stereoconvergent Catalysis from 2005 to 2015: Transition-Metal-Mediated Stereoablative Reactions, Dynamic Kinetic Resolutions, and Dynamic Kinetic Asymmetric Transformations

Palladium‐Catalyzed Decarboxylative Asymmetric Allylic Alkylation: Development, Mechanistic Understanding and Recent Advances

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