New Insight into and Characterization of the Aqueous Metal-Enol(ate) Complexes of (Acetonedicarboxylato)copper

Jefferson, William A.; Hu, Chengzhi; Song, Deying; He, Hao; Qu, Jiuhui

doi:10.1021/acsomega.7b00321

Cited by 4 publications

(1 citation statement)

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“…Oxaloacetic acid(OAA) is a β-keto acid, it plays a central role in several metabolic pathways such as the tricarboxylic acid cycle, gluconeogenesis, fatty acid biosynthesis, amino acid degradation, and amino acid biosynthesis [7][8][9][10][11]. The β-Decarboxylation of oxaloacetate(OA) can be catalyzed by a number of agents including amines [12][13][14][15], enzymes [16][17][18][19][20][21][22], et al Since Krampitz & Werkman reported that Mg( Ⅱ ) can accelerate the decomposition of oxaloacetate [23], many metal ions catalyzed decarboxylation of oxaloacetic acid have been studied [24][25][26][27][28][29][30][31][32][33][34][35][36], a number of multivalent cations (Cu(Ⅱ), Fe(Ⅱ), Co(Ⅱ), Ni(Ⅱ), Zn(Ⅱ), etc.) are shown have good catalytic activity in the ketone decarboxylation.…”

Section: Introductionmentioning

confidence: 99%

Mechanistic Insights into the Decarboxylation of Oxaloacetate Catalyzed by Transition Metal Ions

Song¹,

Fan²

2018

Proceedings of the 8th International Conference on Social Network, Communication and Education (SNCE 2018)

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The decarboxylation mechanism of oxaloacetate catalyzed by transition metal ions M(Ⅱ) (M=Cu, Zn, Co) has been studied using Density Functional Theory (DFT). The calculations show that the catalytic cycle contains two stages: the formation of oxaloacetate-M(Ⅱ) complexes, and the cleavage of the CC bond, the latter one is the rate-determining step in the whole reaction. DFT studies suggest that there are two forms of oxaloacetate dianion, the enol and the keto, the energy barriers for the CC bond cleavage of the three oxaloacetate(enol)-M(Ⅱ) complexes are 89.5(Cu), 261.5(Zn), and 37.5(Co) kJ/mol, and the energy barrier for the keto form of oxaloacetate-M(Ⅱ) complexes are 25.3(Cu), 31.2(Zn) and 63.3(Co) kJ/mol, respectively. The results investigate that the keto form of the oxaloacetate-M(Ⅱ) complexes is easily than the enol form, and Cu(Ⅱ) has better catalytic activity than the other two metal ions. Computational Method All calculations were carried out using B3LYP functional theory[41]. Herein, the metal (copper, zinc, cobalt) atom was treated with the SDD relativistic effective core potential[42-43]. For C, H and O, the

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Section: Introductionmentioning

confidence: 99%

Mechanistic Insights into the Decarboxylation of Oxaloacetate Catalyzed by Transition Metal Ions

Song¹,

Fan²

2018

Proceedings of the 8th International Conference on Social Network, Communication and Education (SNCE 2018)

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1,3‐Acetonedicarboxylic Acid as a Simple Stimulus for Reversible Time‐Controlled pH Modulation

Verdoot,

Quintard

2023

ChemSystemsChem

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Implementation of new activated carboxylic acids is crucial to switch reversibly chemical systems over time in a safer manner. By applying cheap 1,3‐acetonedicarboxylic acid, the pH of aqueous solutions can be decreased before autonomously evolving over time back again to a higher value upon diacid decarboxylation. This decarboxylation can be catalysed by different species such as simple amines or simple metals such as iron and copper salts. This process generates 2 molecules of CO2 and acetone as single waste, considerably decreasing the toxicity associated with such activated acids. The potential of this weak diacid was confirmed by reversibly disrupting a strong gel upon diacid addition and opens the way to the application in complex chemically fuelled systems.

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A Study on N-Substituted Nortropinone Synthesis using Acetone Equivalents

et al. 2020

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Robinson′s synthesis has long been a classic in organic chemistry due to its simplicity and impact in the industry. Various modifications have been made to improve the system. Among them, replacing acetone with more acidic chemical equivalents such as calcium dicarboxylic acid or ethyl dicarboxylic acetone improved the yield. In line with this trend, our group previously reported the synthesis of mono- and di-N-substituted tropinone derivatives from the one-pot reaction of 2,5-dimethoxy tetrahydrofuran and various amines with acetonedicarboxylic acid in the presence of HCl and water at room temperature. In this study, the synthesis with acetone instead of acetone-dicarboxylic acid was examined. Mono- and di-N-substituted nortropinones were prepared in higher yields in all cases although there were extent to which yields increased depending on the nature of substituents

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New Insight into and Characterization of the Aqueous Metal-Enol(ate) Complexes of (Acetonedicarboxylato)copper

Abstract: Nearly 50 years have passed since the classic studies by Larson and Lister [ Larson D. W. Lister M. W. Larson D. W. Lister M. W. Can. J. Chem. 1968 , 46 823 and Hay and Leong [ Hay R. W. Leong K. N. Hay R. W… Show more

Cited by 4 publications

References 54 publications

Mechanistic Insights into the Decarboxylation of Oxaloacetate Catalyzed by Transition Metal Ions

Mechanistic Insights into the Decarboxylation of Oxaloacetate Catalyzed by Transition Metal Ions

1,3‐Acetonedicarboxylic Acid as a Simple Stimulus for Reversible Time‐Controlled pH Modulation

A Study on N-Substituted Nortropinone Synthesis using Acetone Equivalents

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