Models for the active site of vanadium-dependent haloperoxidases: insight into the solution structure of peroxo vanadium compounds

Conte, Valeria; Bortolini, Olga; Carraro, Mauro; Moro, Stefano

doi:10.1016/s0162-0134(00)00038-6

Cited by 85 publications

(66 citation statements)

References 29 publications

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“…The prevalence of the different peroxido complexes is strongly influenced by pH. [31,32] In particular, at pH = 2.5 species with more than one peroxido group bound to the metal are favored, while at pH = 1 the monoperoxido complex is the most abundant species in solution (Scheme 4). Furthermore, the monoperoxido vanadium complex was more reactive than the diperoxido complex toward the oxybromination of alkenes and alkynes; [27,32] recently good results have also been obtained in the benzylic bromination of toluene.…”

Section: Resultsmentioning

confidence: 99%

Thymol Bromination – A Comparison between Enzymatic and Chemical Catalysis

et al. 2015

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An efficient three‐component reaction involving carbon monoxide with a range of aryl bromides and N‐substituted acetoacetamides is reported for the synthesis of β‐keto amides. This transformation is promoted by Pd‐catalysis followed by an acid‐mediated deacetylation upon work‐up, enabling a large number of β‐keto amides to be isolated. Finally, d2‐13C‐dyclonine could be synthesized in three steps utilizing the developed catalytic system as the key step.

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Section: Resultsmentioning

confidence: 99%

Thymol Bromination – A Comparison between Enzymatic and Chemical Catalysis

et al. 2015

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“…Although many model complexes [27,32,33,35,36] have been presented in the literature, the pre-catalytic species K[VO(O 2 )Hheida] [34] isolated by Colpas and co-workers is the most thoroughly investigated system. Detailed mechanistic studies have shown the importance of protonation of the complex with respect to halide [27] and sulfide oxidation.…”

Section: Discussionmentioning

confidence: 99%

Mechanistic Analysis of Nucleophilic Substrates Oxidation by Functional Models of Vanadium‐Dependent Haloperoxidases: A Density Functional Theory Study

et al. 2007

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Density functional theory has been used to investigate the structural, electronic, and reactivity properties of an established functional model for vanadium‐dependent haloperoxidases, K[VO(O2)Hheida] (Hheida2– = 2,2′‐[(2‐hydroxyethyl)imino]diacetate). Possible solution species were determined on the basis of potential exogenous donors present under the conditions necessary for reactivity. The energetically favored solution‐state species is a 1:1 complex of Hheida and vanadium with a coordinated hydroxyethyl donor trans to the vanadium–oxido bond which is in agreement with the reported solid‐state structure for K[VO(O2)Hheida]. Transition states of the oxidation reaction were located for four substrates: chloride, bromide, iodide, and dimethyl sulfide. The role of protonation and its effects on reactivity were examined for each substrate. Protonation of the peroxido moiety leads to a significant drop in the activation barrier for oxidation. In contrast no transition states could be located for an oxido‐transfer process involving the oxido ligand. Barriers of activation calculated for halide oxidation were similar, providing support to the hypothesis that the pKa of the halide in acetonitrile is responsible for the decrease in reactivity between I–, Br–, and Cl–. The results presented herein provide a mechanistic correlation between a functional model and the enzyme, making K[VO(O2)Hheida] a “complete” functional model for vanadium‐dependent haloperoxidase.(© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)

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“…Many different classes of vanadium(V) alkoxides now exist, and the reader is referred to the Cambridge Crystallographic Data Centre [1,[3][4][5][10][11][12][13][14]16,17,[86][87][88][89][90]. The Rosenthal group [91,92] has recently reported an interesting example of this type of chemistry.…”

Section: Fifteen Years Of Dancing With Vanadiummentioning

confidence: 99%

“…11 [44,54,60,80]. 1 H and 13 C NMR spectroscopy have been very useful techniques for studying the solution structure of vanadium(V) complexes [12,14,16,17,41,44,60,72,74,75,80,88,90,95,114]. Both 1D [54] and 2D NMR methods have been very informative with regard to the formation of reaction intermediates [44,120].…”

Section: How Do Vanadium Complexes React In Aqueous Solution?mentioning

confidence: 99%

“…The catalytic and material properties of vanadium compounds and their effects in biological systems have long provided the impetus and fuel to studies of vanadium science [1][2][3][4][5][6][7][8][9][10][11][12][13][14][15][16][17]. Thus far, my group and I have focused on fundamental chemical studies of the various systems in which certain biological responses are observed or anticipated.…”

Section: Introductionmentioning

confidence: 99%

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