Synthesis of α,β‐Unsaturated Ketones by Pd‐Catalyzed Decarboxylative Allylation of α‐Oxocarboxylates

Rodríguez, Nuria; Manjolinho, Filipe; Grünberg, Matthias F.; Gooßen, Lukas J.

doi:10.1002/chem.201102584

Cited by 27 publications

(3 citation statements)

References 61 publications

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“…(1)]. 2a After this seminal work, various sp 2 ‐hybridized carbon derivatives, including allyls,2d,e (hetero)arenes,2f–j enamides,2k and formamides,2l have been successfully acylated using this strategy. However, no example involving sp 3 ‐hybridized carbon centers has been reported. …”

Section: Methodsmentioning

confidence: 99%

Transition‐Metal‐Free Formal Decarboxylative Coupling of α‐Oxocarboxylates with α‐Bromoketones under Neutral Conditions: A Simple Access to 1,3‐Diketones

et al. 2014

Angew Chem Int Ed

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A transition-metal-free formal decarboxylative coupling reaction between α-oxocarboxylates and α-bromoketones to synthesize 1,3-diketone derivatives is presented. In this reaction, a broad scope of substrates can be employed, and neither a metal-based reagent nor an additional base is required. DFT calculations reveal that this reaction proceeds through a coupling followed by decarboxylation mechanism and the α-bromoketone unprecedentedly serves as a nucleophile under neutral conditions. The rate-determining step is an unusual hydrogen-bond-assisted enolate formation by thermolysis.

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Section: Methodsmentioning

confidence: 99%

Transition‐Metal‐Free Formal Decarboxylative Coupling of α‐Oxocarboxylates with α‐Bromoketones under Neutral Conditions: A Simple Access to 1,3‐Diketones

et al. 2014

Angew Chem Int Ed

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“…Recently, increasing use of nitrobenzoic acid derivatives in palladium-catalyzed decarboxylative cross-coupling reactions has also motivated us to explore the ortho -allylation reaction. Although palladium-catalyzed decarboxylative sp 3 –sp 3 allylic alkylation has been widely explored, decarboxylative sp 2 –sp 3 allylation is less studied . In this vein, an activated coumarin moiety furnished moderate to good yields of allylation product and preferred sp 3 –sp 3 allylation over the sp 2 –sp 3 allylation .…”

mentioning

confidence: 99%

Palladium(0)-Catalyzed Intramolecular Decarboxylative Allylation of Ortho Nitrobenzoic Esters

2014

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A Pd/Ag bimetallic system has been developed for the decarboxylative allylation of ortho-nitrobenzoic esters in an intramolecular fashion. In contrast to the typical sp(2)-sp(3) cross-coupling approach which requires air and moisture sensitive preformed organometallic reagents, we provide an alternative route to the synthesis of ortho-allyl nitroarenes from the corresponding ortho-nitrobenzoic acid derivatives. The reaction proceeds through a mechanistically distinct decarboxylative metalation pathway. A cooperative reactivity of palladium and silver is crucial for the reaction outcome.

show abstract

Section: Methodsmentioning

confidence: 99%

Transition‐Metal‐Free Formal Decarboxylative Coupling of α‐Oxocarboxylates with α‐Bromoketones under Neutral Conditions: A Simple Access to 1,3‐Diketones

et al. 2014

Angewandte Chemie

View full text Add to dashboard Cite

A transition-metal-free formal decarboxylative coupling reaction between a-oxocarboxylates and a-bromoketones to synthesize 1,3-diketone derivatives is presented. In this reaction, a broad scope of substrates can be employed, and neither a metal-based reagent nor an additional base is required. DFT calculations reveal that this reaction proceeds through a coupling followed by decarboxylation mechanism and the a-bromoketone unprecedentedly serves as a nucleophile under neutral conditions. The rate-determining step is an unusual hydrogen-bond-assisted enolate formation by thermolysis.

show abstract

Synthesis of α,β‐Unsaturated Ketones by Pd‐Catalyzed Decarboxylative Allylation of α‐Oxocarboxylates

Cited by 27 publications

References 61 publications

Transition‐Metal‐Free Formal Decarboxylative Coupling of α‐Oxocarboxylates with α‐Bromoketones under Neutral Conditions: A Simple Access to 1,3‐Diketones

Transition‐Metal‐Free Formal Decarboxylative Coupling of α‐Oxocarboxylates with α‐Bromoketones under Neutral Conditions: A Simple Access to 1,3‐Diketones

Palladium(0)-Catalyzed Intramolecular Decarboxylative Allylation of Ortho Nitrobenzoic Esters

Transition‐Metal‐Free Formal Decarboxylative Coupling of α‐Oxocarboxylates with α‐Bromoketones under Neutral Conditions: A Simple Access to 1,3‐Diketones

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