- The formyloxyl radical: Electrophilicity, C-H bond activation and anti-Markovnikov selectivity in the oxidation of aliphatic alkenes
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In the past the formyloxyl radical, HC(O)O, had only been rarely experimentally observed, and those studies were theoretical-spectroscopic in the context of electronic structure. The absence of a convenient method for the preparation of the formyloxyl radical has precluded investigations into its reactivity towards organic substrates. Very recently, we discovered that HC(O)O is formed in the anodic electrochemical oxidation of formic acid/lithium formate. Using a [CoIIIW12O40]5- polyanion catalyst, this led to the formation of phenyl formate from benzene. Here, we present our studies into the reactivity of electrochemically in situ generated HC(O)O with organic substrates. Reactions with benzene and a selection of substituted derivatives showed that HC(O)O is mildly electrophilic according to both experimentally and computationally derived Hammett linear free energy relationships. The reactions of HC(O)O with terminal alkenes significantly favor anti-Markovnikov oxidations yielding the corresponding aldehyde as the major product as well as further oxidation products. Analysis of plausible reaction pathways using 1-hexene as a representative substrate favored the likelihood of hydrogen abstraction from the allylic C-H bond forming a hexallyl radical followed by strongly preferred further attack of a second HC(O)O radical at the C1 position. Further oxidation products are surmised to be mostly a result of two consecutive addition reactions of HC(O)O to the CC double bond. An outer-sphere electron transfer between the formyloxyl radical donor and the [CoIIIW12O40]5- polyanion acceptor forming a donor-acceptor [D+-A-] complex is proposed to induce the observed anti-Markovnikov selectivity. Finally, the overall reactivity of HC(O)O towards hydrogen abstraction was evaluated using additional substrates. Alkanes were only slightly reactive, while the reactions of alkylarenes showed that aromatic substitution on the ring competes with C-H bond activation at the benzylic position. C-H bonds with bond dissociation energies (BDE) ≤ 85 kcal mol-1 are easily attacked by HC(O)O and reactivity appears to be significant for C-H bonds with a BDE of up to 90 kcal mol-1. In summary, this research identifies the reactivity of HC(O)O towards radical electrophilic substitution of arenes, anti-Markovnikov type oxidation of terminal alkenes, and indirectly defines the activity of HC(O)O towards C-H bond activation.
- Iron, Mark A.,Khenkin, Alexander M.,Neumann, Ronny,Somekh, Miriam
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p. 11584 - 11591
(2020/11/23)
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- Hollow Carbon Sphere Nanoreactors Loaded with PdCu Nanoparticles: Void-Confinement Effects in Liquid-Phase Hydrogenations
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Nanoreactors with hollow structures have attracted great interest in catalysis research due to their void-confinement effects. However, the challenge in unambiguously unraveling these confinement effects is to decouple them from other factors affecting catalysis. Here, we synthesize a pair of hollow carbon sphere (HCS) nanoreactors with presynthesized PdCu nanoparticles encapsulated inside of HCS (PdCu?HCS) and supported outside of HCS (PdCu/HCS), respectively, while keeping other structural features the same. Based on the two comparative nanoreactors, void-confinement effects in liquid-phase hydrogenation are investigated in a two-chamber reactor. It is found that hydrogenations over PdCu?HCS are shape-selective catalysis, can be accelerated (accumulation of reactants), decelerated (mass transfer limitation), and even inhibited (molecular-sieving effect); conversion of the intermediate in the void space can be further promoted. Using this principle, a specific imine is selectively produced. This work provides a proof of concept for fundamental catalytic action of the hollow nanoreactors.
- Dong, Chao,Liu, Jian,Su, Panpan,Wang, Guang-Hui,Ye, Run-Ping,Yu, Qun
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supporting information
p. 18374 - 18379
(2020/08/19)
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- Microbial synthesis of plant oxylipins from γ-linolenic acid through designed biotransformation pathways
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Secondary metabolites of plants are often difficult to synthesize in high yields because of the large complexity of the biosynthetic pathways and challenges encountered in the functional expression of the required biosynthetic enzymes in microbial cells. In this study, the biosynthesis of plant oxylipins - a family of oxygenated unsaturated carboxylic acids - was explored to enable a high-yield production through a designed microbial synthetic system harboring a set of microbial enzymes (i.e., fatty acid double-bond hydratases, alcohol dehydrogenases, Baeyer-Villiger monooxygenases, and esterases) to produce a variety of unsaturated carboxylic acids from γ-linolenic acid. The whole cell system of the recombinant Escherichia coli efficiently produced (6Z,9Z)-12-hydroxydodeca-6,9-dienoic acid (7), (Z)-9-hydroxynon-6-enoic acid (15), (Z)-dec-4-enedioic acid (17), and (6Z,9Z)-13-hydroxyoctadeca-6,9-dienoic acid (2). This study demonstrated that various secondary metabolites of plants can be produced by implementing artificial biosynthetic pathways into whole-cell biocatalysis.
- Kim, Sae-Um,Kim, Kyoung-Rok,Kim, Ji-Won,Kim, Soomin,Kwon, Yong-Uk,Oh, Deok-Kun,Park, Jin-Byung
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p. 2773 - 2781
(2015/03/30)
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- Chiral Co(II) metal-organic framework in the heterogeneous catalytic oxidation of alkenes under aerobic and anaerobic conditions
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The chiral Co(II) MOF [Co(l-RR)(H2O)·H2O] ∞ [1; l-RR = (R,R)-thiazolidine-2,4-dicarboxylate] has been exploited in the catalytic oxidation of different alkenes (cyclohexene, (Z)-cyclooctene, 1-octene) using either tert-butyl hydroperoxide ( tBuOOH) or molecular oxygen (O2) as oxidants. Different chemoselectivities are observed, both substrate- and oxidant-dependent. A moderate enantioselectivity is also obtained in the case of prochiral precursors, revealing the chiral induction ability of the optically pure metal environment. The interaction of O2 with the exposed metal sites in 1 (after material preactivation and consequent removal of the coordinated aquo ligand) has been studied through TPD-MS analysis combined with DFT calculations, with the aim of probing effective oxygen uptake by the heterogeneous catalyst and unraveling the nature of the active species in the catalytic oxidation process under aerobic conditions. Theoretical results indicate the presence of an η1-superoxo species at the cobalt center, with concomitant Co(II) ? Co(III) oxidation. Finally, the experimental estimation of the O2 adsorption enthalpy is found to be in good agreement with the calculated binding energy.
- Tuci, Giulia,Giambastiani, Giuliano,Kwon, Stephanie,Stair, Peter C.,Snurr, Randall Q.,Rossin, Andrea
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p. 1032 - 1039
(2014/04/03)
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- Structure and characteristics of chitosan cobalt-containing hybrid systems, the catalysts of olefine oxidation
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Cobalt-containing hybrid organo-inorganic materials based on the chitosan-SiO2, chitosan-Al2O3, and chitosan-cellulose systems were obtained. The surface structure and processes that occur during the formation of metal-containing materials, the catalytic properties of which were studied in the oxidation reactions of alkene, were investigated by EPR spectroscopy using a stable pH-sensitive nitroxyl radical, 4-dimethylamino-2-ethyl-5,5-dimethyl-2-(pyridin-4-yl)-2,5-dihydro-1H-imidazole- 1-oxyl, as the adsorbed probe molecules.
- Mekhaev,Pestov,Molochnikov,Kovaleva,Pervova,Yaltuk, Yu. G.,Grigor'Ev,Kirilyuk
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experimental part
p. 1155 - 1161
(2011/08/05)
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- Nanocrystalline ZSM-5: A catalyst with high activity and selectivity for epoxide rearrangement reactions
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Nanocrystalline ZSM-5 (~20-50 nm) has been tested as a catalyst in the liquid phase rearrangement of 1,2-epoxyoctane, 2-methyl-2,3-epoxybutane and isophorone oxide together with a microcrystalline ZSM-5 sample (~5 μm) employed as a reference. Whereas this last material shows a low activity for the three epoxide rearrangement reactions considered, nanocrystalline ZSM-5 leads in all cases to high epoxide conversion. This different catalytic performance is attributed to the differences in the accessibility of the reactant molecules to the catalyst active sites. The smallest crystal size of the nanocrystalline zeolite contributes favourably to both the formation of a high external surface area, with no steric constraints, and to a faster intracrystalline diffusion of the epoxide molecules towards the acid sites located within the zeolite micropores. When sterically hindered epoxides are tested, the catalytic rearrangement occurs mainly on the external surface of the nanocrystalline zeolite. Moreover, it is remarkable that for the three epoxides investigated the high catalytic activity observed over nanocrystalline ZSM-5 is accompanied by the attainment of high selectivities, typically around or over 80%, towards products with commercial applications.
- Serrano, David P.,van Grieken, Rafael,Melero, Juan Antonio,García, Alicia,Vargas, Carolina
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scheme or table
p. 68 - 74
(2010/06/16)
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- PpoC from Aspergillus nidulans is a fusion protein with only one active haem
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In Aspergillus nidulans Ppos [psi (precocious sexual inducer)-producing oxygenases] are required for the production of so-called psi factors, compounds that control the balance between the sexual and asexual life cycle of the fungus. The genome of A. nidulans harbours three different ppo genes: ppoA, ppoB and ppoC. For all three enzymes two different haem-containing domains are predicted: a fatty acid haem peroxidase/ dioxygenase domain in the N-terminal region and a P450 haem-thiolate domain in the C-terminal region. Whereas PpoA was shown to use both haem domains for its bifunctional catalytic activity (linoleic acid 8-dioxygenation and 8-hydroperoxide isomerization), we found that PpoC apparently only harbours a functional haem peroxidase/dioxygenase domain. Consequently, we observed that PpoC catalyses mainly the dioxygenation of linoleic acid (18:2Δ 9Z,12Z), yielding 10-HPODE (10-hydroperoxyoctadecadienoic acid). No isomerase activity was detected. Additionally, 10-HPODE was converted at lower rates into 10-KODE (10-keto-octadecadienoic acid) and 10-HODE (10-hydroxyoctadecadienoic acid). In parallel, decomposition of 10-HPODE into 10-ODA (10-octadecynoic acid) and volatile C-8 alcohols that are, among other things, responsible for the characteristic mushroom flavour. Besides these principle differences we also found that PpoA and PpoC can convert 8-HPODE and 10-HPODE into the respective epoxy alcohols: 12,13-epoxy-8-HOME (where HOME is hydroxyoctadecenoic acid) and 12,13-epoxy-10-HOME. By using site-directed mutagenesis we demonstrated that both enzymes share a similar mechanism for the oxidation of 18:2Δ9Z,12Z; they both use a conserved tyrosine residue for catalysis and the directed oxygenation at the C-8 and C-10 is most likely controlled by conserved valine/leucine residues in the dioxygenase domain. The Authors Journal compilation
- Brodhun, Florian,Schneider, Stefan,Goebel, Cornelia,Hornung, Ellen,Feussner, Ivo
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experimental part
p. 553 - 565
(2011/02/23)
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