Search results for "Activity"

Quadruply-bonded dimolybdenum compounds: Reactivity towards TCNE. Structural evidences for the 1-D polymer [Mo2(O2 CCF3)4(TCNE)]∞

2005

cited By 3; International audience; Reaction of [Mo2(O2CR)4] (R = CF 3, 1) with TCNE in toluene affords the new compound [Mo2(O2CCF3)4 (TCNE)·6H5CH3 (2). The structure of 2 is built on [Mo2(O2 CCF3)4] fragments having the usual paddlewheel structure of 1 (Mo-Mo 2.1117(8) Å) and TCNE units. Each polynitrile moiety acts as a bridging ligand between two Mo2 fragments (Mo-N 2.875(4) Å) affording 1-D polymeric chains crossing in the crystal; the toluene molecules occupy the cavities between the chains. 13C NMR, IR and electrochemical data clearly show that formation of 2 does not involve electron density transfer from dimolybdenum fragment to the TCNE unit, which remains in 2 in its neutral stat…

Glutathione Peroxidase Activity and Selenium Therapy in Muscular Dystrophies

1988

Preparation of dithiacycloalkynes by cyclization reactions applying the cesium effect

1993

Abstract The strained dithiacycloalkynes 3a,b and the larger heterocyclic alkynes 3c and 4 are obtained by cesium assisted cyclization reactions of the dithiols 1a–c and 1,4-dibromo-2-butyne (2). The reactivity of 3a–c was studied in cycloaddition and complexation reactions generating the adducts 5a,b and 6 and the silver and cobalt complexes 7 and 8.

High pressure processing of food-grade emulsion systems: Antimicrobial activity, and effect on the physicochemical properties

2019

Abstract The use of high pressure processing (HPP) for development of stable emulsion-based delivery systems has been recently increased. Under adequate conditions, application of high pressures modifies the functionality of protein and polysaccharide molecules and significantly promotes the emulsifying activities. Application of high pressures also modulates the emulsion microstructure without any destabilization and gelation of protein molecules. The lipid oxidation in HPP-treated emulsions can be accelerated, particularly with higher pressure levels, while the HPP utilization on emulsions in acidic conditions can highly inhibit the growth of spoilage and pathogenic microorganisms. In thi…

Theoretical study of the regio- and stereoselectivity of the intramolecular Povarov reactions yielding 5H-chromeno[2,3-c] acridine derivatives

2016

The intramolecular Povarov (IMP) reactions involved in the synthesis of 5H-chromeno[2,3-c] acridine derivatives [Tetrahedron Lett., 2010, 51, 3071–3074] have been studied using density functional theory (DFT) methods. The studied IMP reaction is a domino process that comprises two consecutive reactions: (i) a BF3 Lewis acid catalysed intramolecular aza-Diels–Alder (IMADA) reaction of an alkene tethered chromene imine (ATCI) giving a formal [4 + 2] cycloadduct, and (ii) a 1,3-hydrogen shift yielding the final chromeno product. The possible regio-(fused/bridged) and stereo-(cis/trans) isomeric channels associated with the IMADA reaction were thoroughly investigated and analysed. The activatio…

Iron-catalyzed C(sp2)-C(sp3) cross-coupling at low catalyst loading

2019

The iron-catalyzed C(sp2)–C(sp3) cross-coupling provides a highly economical route to exceedingly valuable alkylated arenes that are widespread in medicinal chemistry and materials science. Herein, we report an operationally-simple protocol for the selective C(sp2)–C(sp3) iron-catalyzed cross-coupling of aryl chlorides with Grignard reagents at low catalyst loading. A broad range of electronically-varied aryl and heteroaryl chlorides underwent the cross-coupling using challenging alkyl organometallics possessing β-hydrogens with high efficiency up to 2000 TON. A notable feature of the protocol is the use of environmentally-friendly cyclic urea ligands. A series of guidelines to predict cros…

Reactivity of lithium β‑ketocarboxylates: the role of lithium salts

2017

Lithium beta-ketocarboxylates 1(COOLi), prepared by the reaction of lithium enolates 2(Li+) with carbon dioxide, readily decarboxylate in THF solution unless in the presence of lithium salts, in which case they are indefinitely stable at room temperature in inert atmosphere. The availability of stable THF solutions of lithium beta-ketocarboxylates 1(COOLi) in the absence of carbon dioxide allowed reactions to take place with nitrogen bases and alkyl halides 3 to give alpha-alkyl ketones 1(R) after acidic hydrolysis. The sequence thus represents the use of carbon dioxide as a removable directing group for the selective monoalkylation of lithium enolates 2(Li+). The roles of lithium salts in …

Lithium Cation-Catalyzed Benzene Diels-Alder Reaction: Insights on the Molecular Mechanism Within the Molecular Electron Density Theory.

2020

The lithium cation Li+-catalyzed Diels-Alder (DA) reactions of benzene toward a series of acetylenes of improved nucleophilicity can be described within the context of the molecular electron density theory (MEDT) at the ωB97XD/6-311G(d,p) level. Conceptual density functional theory indices characterize the crown ether solvated complex benzene-lithium Bz-Li-Cro as a superelectrophile. Coordination of a lithium cation to benzene does not change substantially the electron localization function electronic structure of benzene. The DA reaction of Bz-Li-Cro with acetylene shows a reduction of the energy of activation of 6.9 kcal·mol-1, which is not sufficient for the reaction to take place, thus …

Theoretical Studies of the Reactivity of Cyclopentadienyl Nitrosyl Alkyl Species of Molybdenum and Tungsten

2000

International audience; The reactivity differences observed experimentally for Cp*W(NO)(CH2CMe3)2 and CpMo(NO)(CH2CMe3)2 have been investigated using density functional theory (DFT) techniques. The reactions of the CpW(NO)(CH2) model complex with NH3 and CH4 are more exothermic and have lower activation barriers than the corresponding processes for CpMo(NO)(CH2). The η2(C,H) methane complex CpM(NO)(CH2)(CH4) (M = Mo, W) can undergo two competitive processes:  C−H activation to afford CpM(NO)(CH3)2 or loss of methane. The relative barrier heights are almost identical for M = W, whereas the formation of CpM(NO)(CH3)2 is significantly disfavored for M = Mo. The activation of C−H and N−H bonds …

Influence of the Ligand of Palladium(0) Complexes on the Rate of the Oxidative Addition of Aryl and Activated Alkyl Bromides: Csp2 −Br versus Csp3 −B…

2017

Kinetic data by means of electrochemical techniques are used to characterize the reactivity of aryl bromides and activated alkyl bromides in oxidative addition to palladium(0) complexes generated from three precursors: Pd0(PPh3)4, {Pd0(dba)2 + 2 PPh3} and {Pd0(dba)2 + 2 P(o Tol)3} in DMF at 25 °C. It is established that, for the investigated substrates 1-6 and 7-11, the oxidative addition at the Csp3 Br bond is much faster than that at the Csp2 Br bond when the palladium(0) is ligated by two PPh3. This explains why the regioselectivity in Suzuki-Miyaura reactions performed from substrates bearing both Csp2 Br and Csp3 Br groups is in favour of the substitution at the Csp3 Br bond. It is in …