Dioxygen activation and two consecutive oxidative decarboxylations of phenylpyruvate by nonheme iron(<scp>ii</scp>) complexes: functional models of hydroxymandelate synthase (HMS) and CloR

Sheet, Debobrata; Bhattacharya, S.; Paine, Tapan Kanti

doi:10.1039/c5cc01652e

Cited by 12 publications

(16 citation statements)

References 32 publications

(58 reference statements)

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The initial coordinates of the function model molecule were obtained from Cambridge Crystallographic Data Centre (CCDC), in which the histidine residues were simplified as analogues of imidazole . All the calculations were performed with Gaussian 03 program packages at B3LYP/LACVP* computational level, which was credible and successfully used previously .…”

Section: Computational Detailsmentioning

confidence: 99%

“…All the calculations were performed with Gaussian 03 program packages at B3LYP/LACVP* computational level, which was credible and successfully used previously . The self‐consistent reaction field (SCRF) calculations in the polarizable continuum model (PCM) were employed to obtain all the stationary points, and an acetonitrile solvent was taken to meet the experimental conditions . The most stable conformations of the reactants, transition states, intermediates, and products as well as their energies at equilibrium structures have been figured out.…”

Section: Computational Detailsmentioning

confidence: 99%

“…Three substrates were requisite to complete the catalytic process, including a molecule of α‐ketoglutarate type, a catalytic substrate, and the O 2 molecule. To explore the details of the CC bond cleavage for hydroxyphenyl‐pyruvate, a number of function models have been synthesized and investigated . The research data implicated a mechanism with two consequent oxidative decarboxylations, and the substrates would be activated by dioxygen and some ferryl species.…”

Section: Introductionmentioning

confidence: 99%

“…But it was still unclear on the details of how they worked. An intermediate characterized with a five‐membered ring and an iron‐superoxide compound were found in several proposed mechanisms . Furthermore, an epoxide was identified as the product of hydroxylation by means of a theoretical study, and a high‐spin Fe(III)/ring was proposed to be generated after an electrophilic attack.…”

Section: Introductionmentioning

confidence: 99%

See 3 more Smart Citations

A Theoretical Study on the Mechanism of Decarboxylations for Hydroxymandelate Synthase

Qiao

Liu

et al. 2017

Bulletin Korean Chem Soc

View full text Add to dashboard Cite

Hydroxymandelate synthase is one type of alpha‐keto acid‐dependent oxygenases and plays an important role in the biosynthesis of hydroxyphenyl‐pyruvate. The ferrous and ferryl intermediates in the reaction were considered to be very important in the DNA repair process. The mechanism of hydroxymandelate synthase was investigated by a theoretical method based on B3LYP/LACVP*. The data indicated that each decarboxylation went through a process of direct dioxygen insertion. The first oxidative decarboxylation experienced only one transition state, while there were two potential pathways for the second decarboxylation process. The calculation data showed that the stepwise one was favored to the concerted one due to the lower energy barrier. The process to form the iron‐superoxide was the rate‐limiting step. After two consecutive decarboxylations, a proton transfer reaction was needed to obtain the target products. Two possible transition states were found out to achieve this step. The one with a six‐membered ring structure was preferred because of the lower activation energy. In addition, several ferryl species with high spins were captured in the whole process, which could be supplied as requisite substrates for DNA repair reaction.

show abstract

Section: Computational Detailsmentioning

confidence: 99%

Section: Computational Detailsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

A Theoretical Study on the Mechanism of Decarboxylations for Hydroxymandelate Synthase

Qiao

Liu

et al. 2017

Bulletin Korean Chem Soc

View full text Add to dashboard Cite

show abstract

“…On the basis of studies with Fe(II)-HMA model complexes (R = H, Fig. 1a) [37-39], the mechanism shown in Fig. 1d has been proposed for the second oxidation to produce 3DMA-HB.…”

Section: Spring-loaded Substrates: Hppd Hms and Clormentioning

confidence: 99%

Go it alone: four-electron oxidations by mononuclear non-heme iron enzymes

Peck

Donk

2016

J Biol Inorg Chem

View full text Add to dashboard Cite

Carbon‐Nanotube‐Appended PAMAM Dendrimers Bearing Iron(II) α‐Keto Acid Complexes: Catalytic Non‐Heme Oxygenase Models

Sheet

Bera

et al. 2019

Chemistry A European J

Self Cite

View full text Add to dashboard Cite

Poly(amidoamine) dendrimers grafted on carbon nanotubes have been appended with iron(II)‐α‐keto acid (benzoylformate) complex of polypyridyl ligand to design artificial non‐heme oxygenase model. This nano‐enzyme was applied for selective catalytic oxidation of organic molecules. Although the carbon nanotubes serve as a robust heterogeneous platform, the amine terminals of dendrimers provide catalysts binding sites and the amide bonds provide a necessary second coordination sphere similar to the enzymatic polypeptide chains. Such a hybrid design prevented the deactivation of the primary active sites leading to 8 times faster oxidative decarboxylation rates than those of its homogeneous analogue. An electrophilic iron(IV)‐oxo intermediate has been intercepted, which catalyzes the selective oxidation of alcohols to aldehydes and incorporates single oxygen atoms into sulfides and olefins by using aerial oxygen with multiple turnover numbers. The catalyst was consecutively regenerated three times by mild chemical treatment and showed negligible loss of activity.

show abstract

Dioxygen activation and two consecutive oxidative decarboxylations of phenylpyruvate by nonheme iron(ii) complexes: functional models of hydroxymandelate synthase (HMS) and CloR

Abstract: Two mononuclear iron(ii)-phenylpyruvate complexes of monoanionic facial N3 ligands are reported to react with dioxygen to undergo two consecutive oxidative decarboxylation steps via an iron-mandelate complex mimicking the function of HMS and CloR.

Cited by 12 publications

References 32 publications

A Theoretical Study on the Mechanism of Decarboxylations for Hydroxymandelate Synthase

A Theoretical Study on the Mechanism of Decarboxylations for Hydroxymandelate Synthase

Go it alone: four-electron oxidations by mononuclear non-heme iron enzymes

Carbon‐Nanotube‐Appended PAMAM Dendrimers Bearing Iron(II) α‐Keto Acid Complexes: Catalytic Non‐Heme Oxygenase Models

Contact Info

Product

Resources

About