Catalysis of the Decarboxylation of Dimethyloxaloacetate by Manganese(II), Nickel(II), and Their Complexes

Rund, John V.; Plane, Robert A.

doi:10.1021/ja01057a016

Cited by 33 publications

(19 citation statements)

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“…61 Moreover, Darensbourg suggests that coordination of the ketone oxygen may facilitate decarboxylation by allowing the formation of M-bound enolate as opposed to a “free” enolate ( D ). 13,60 Applying these observations to palladium-catalyzed decarboxylation of β-oxo esters suggests that an ionic mechanism for decarboxylation is favored over the cyclic transition state favored for decarboxylation of β-keto acids. While ionic mechanisms may not seem favorable for decarboxylations in non-polar solvents, it is known that non-polar solvents increase the rates of related decarboxylations.…”

Section: Mechanistic Aspects Of the Dca Of Enolatesmentioning

confidence: 90%

“…In the early 60’s, divalent metals like Ni(II) and Mn(II) were shown to decarboxylate malonic acids and were proposed to form intermediate metal enolates. 13 While the knowledge of these transformations was applied to understanding enzymatic decarboxylations, the synthetic potential of the intermediates was not realized.…”

Section: Decarboxylative Allylation Of Enolatesmentioning

confidence: 99%

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Transition Metal-Catalyzed Decarboxylative Allylation and Benzylation Reactions

et al. 2011

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Section: Mechanistic Aspects Of the Dca Of Enolatesmentioning

confidence: 90%

Section: Decarboxylative Allylation Of Enolatesmentioning

confidence: 99%

Transition Metal-Catalyzed Decarboxylative Allylation and Benzylation Reactions

et al. 2011

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“…Effective ligands are 2,2'-bipyridyl [37], 1,lO-phenanthroline [38,39], and pyridine [40] ; they all contain n-systems. Of interest in this connection is also that the hydrolysis of diisopropyl fluorophosphate is catalyzed by several Cu2+ complexes, among which the Cu2+-bipyridyl I : 1 complex is especially effective.…”

Section: Discussionmentioning

confidence: 99%

Ternary Complexes in Solution

Huber

Griesser

Prijs

et al. 1969

European Journal of Biochemistry

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The stability constants of the ternary Cuz+ complexes, ethylenediamine-Cu2+-pyrocatechol and histamine-Cua+-pyrocatechol dianion, were determined. Both complexes are more stable than one would expect on pure statistical reasons. The imidazole-containing ternary Cuz+ complex is, however, especially stable. For the equilibrium, Cu(histamine), + Cu(pyrocatechol), ~2[(histamine)Cu(pyrocatechol)], the constant is log X = 4.86 (I = 0.1; T = 25"), while the statistical value is 0.6. These results were compared with those taken (or calculated) from the literature; it is concluded that the n-system of the ligands is important for such a great increase in stability. Furthermore, the Cuz+-histamine I : 1 complex selectively binds to 0-ligands rather than to N-ligands. Thus, the first coordinated ligand has an influence on the kind of the second to be coordinated, i. e. the Cua+-histamine 1 : 1 complex shows discriminating qualities. The significance of these results is discussed with regard to Cu-proteins, since it is suggested for several enzymes that the imidazole group of histidine is involved with the binding of metal ions.I n general, ternary complexes, i.e. mixed ligand metal ion complexes, can be considered as models [2] for enzyme-metal ion-substrate complexes [3,4]. Furthermore, such ternary complexes probably occur in biological fluids that contain several ligands as well as different metal ions. Investigations of the stability of ternary complexes may, therefore, help toward understanding the driving forces which lead to the formation of such complexes in biological systems. The importance of mixed complexes in nature is evident, since a great deal of biochemical reactions occur in such complexes, i.e. within the coordination sphere of metal ions [3,4].I n addition, the investigation of ternary Cu2+ complexes, containing an imidazole group as binding site, is of special interest, since it is suggested for several proteins which interact with Cua+ and for natural Cu-proteins that the imidazole group of histidine binds to copper. Thus, the Cuz+ complexes of several histidine-containing peptides

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“…Ionization of metal carboxylates, which has been suggested to occur readily with Pd, is understood to promote decarboxylation (Figure , mechanism A) . Coordination of Pd to the ketone oxygen leading to a metal bound enolate can also facilitate decarboxylation (Figure , mechanism B) . Tunge has described the possible mechanistic pathways for the decarboxylative step for β‐ketocarboxylates and allyl enol carbonates in considerable detail, concluding that “assessment of the true pathway for decarboxylation will require more detailed experimentation” …”

Section: Mechanistic Investigations Into Pd‐catalyzed Daaamentioning

confidence: 99%

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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Catalysis of the Decarboxylation of Dimethyloxaloacetate by Manganese(II), Nickel(II), and Their Complexes

Cited by 33 publications

References 0 publications

Transition Metal-Catalyzed Decarboxylative Allylation and Benzylation Reactions

Transition Metal-Catalyzed Decarboxylative Allylation and Benzylation Reactions

Ternary Complexes in Solution

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

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