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showing 10 items of 14566 documents

Bond Dissociation Energies for Diatomic Molecules Containing 3d Transition Metals: Benchmark Scalar-Relativistic Coupled-Cluster Calculations for 20 …

2017

Benchmark scalar-relativistic coupled-cluster calculations for dissociation energies of the 20 diatomic molecules containing 3d transition metals in the 3dMLBE20 database ( J. Chem. Theory Comput. 2015 , 11 , 2036 ) are reported. Electron correlation and basis set effects are systematically studied. The agreement between theory and experiment is in general satisfactory. For a subset of 16 molecules, the standard deviation between computational and experimental values is 9 kJ/mol with the maximum deviation being 15 kJ/mol. The discrepancies between theory and experiment remain substantial (more than 20 kJ/mol) for VH, CrH, CoH, and FeH. To explore the source of the latter discrepancies, the …

010304 chemical physicsElectronic correlationChemistryThermodynamics010402 general chemistry01 natural sciencesDiatomic moleculeHeterolysisBond-dissociation energyDissociation (chemistry)0104 chemical sciencesComputer Science ApplicationsCoupled cluster0103 physical sciencesMoleculePhysical and Theoretical ChemistryAtomic physicsBasis setJournal of Chemical Theory and Computation
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Approximate treatment of higher excitations in coupled-cluster theory. II. Extension to general single-determinant reference functions and improved a…

2008

The theory and implementation of approximate coupled-cluster (CC), in particular approximate CC singles, doubles, triples, and quadruples methods, are discussed for general single-determinant reference functions. While the extension of iterative approximate models to the non-Hartree-Fock case is straightforward, the generalization of perturbative approaches is not trivial. In contrast to the corresponding perturbative triples methods, there are additional terms required for non-Hartree-Fock reference functions, and there are several possibilities to derive approximations to these terms. As it turns out impossible to develop an approach that is consistent with the canonical Hartree-Fock-base…

010304 chemical physicsGeneralizationHartree–Fock methodGeneral Physics and AstronomyContrast (statistics)Extension (predicate logic)010402 general chemistry01 natural sciences0104 chemical sciencesCoupled clusterComputational chemistry0103 physical sciencesApplied mathematicsPerturbation theory (quantum mechanics)Physical and Theoretical ChemistryMathematicsThe Journal of Chemical Physics
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A solvent-directed stereoselective and electrocatalytic synthesis of diisoeugenol.

2018

A stereoselective and electrocatalytic coupling reaction of isoeugenol has been reported for the first time in a 1,1,1,3,3,3-hexafluoro-2-propanol (HFIP)/boron-doped diamond (BDD) electrode system. This particular C-C bond formation and diastereoselectivity is driven by a solvate interaction between the radical species and another isoeugenol molecule. Due to an electrocatalytic cycle, only understoichiometric amounts of charge are necessary. Since electric current is directly employed as the oxidant, the reaction is metal and reagent-free. In addition, the electrolysis can be conducted in a very simple undivided beaker-type cell under constant current conditions. Therefore, the protocol is …

010402 general chemistry01 natural sciencesCatalysisCoupling reactionlaw.inventionMetalchemistry.chemical_compoundlawMaterials ChemistryMoleculeElectrolysis010405 organic chemistryMetals and AlloysGeneral ChemistryCombinatorial chemistry0104 chemical sciencesSurfaces Coatings and FilmsElectronic Optical and Magnetic MaterialsSolventIsoeugenolchemistryvisual_artElectrodeCeramics and Compositesvisual_art.visual_art_mediumStereoselectivityChemical communications (Cambridge, England)
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A concise route to MK-4482 (EIDD-2801) from cytidine.

2020

A two-step route to MK-4482 (EIDD-2801, 1) was developed consisting of an esterification and hydroxamination of cytidine. The selective acylation and direct amination eliminate the need for protecting and activating groups and proceed in overall yield of 75%, a significant advancement over the reported yield of 17%. The step count is reduced from five transformations to two, and expensive uridine is replaced with the more available cytidine.

010405 organic chemistryAcylationMetals and AlloysCytidineGeneral ChemistryCytidine010402 general chemistryHydroxylamines01 natural sciencesCombinatorial chemistryCatalysisUridine0104 chemical sciencesSurfaces Coatings and FilmsElectronic Optical and Magnetic MaterialsAcylationchemistry.chemical_compoundKineticschemistryYield (chemistry)Materials ChemistryCeramics and CompositesStep countAminationChemical communications (Cambridge, England)
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First copper(I) ferrocenyltetraphosphine complexes: possible involvement in Sonogashira cross-coupling reaction ?

2008

Preparation and characterization of the first examples of copper(I) ferrocenylpolyphosphine complexes are reported. The molecular structure of complex {P,P′,P′′-[1,1′,2,2′-tetrakis(diphenylphosphino)-4,4′-di-tert-butylferrocene]iodocopper(I)} (1) was solved by X-ray diffraction studies, and its fluxional behavior in solution was investigated by VT-31P NMR; both revealed a net triligated coordination preference of the ferrocenyl tetraphosphine Fc(P)4tBu with copper. The tetradentate ligand is an active auxiliary in Sonogashira alkynylation; therefore the general question of copper as a competitive coordination partner in the Pd/Cu-catalyzed Sonogashira reaction was raised and discussed. Elec…

010405 organic chemistryArylOrganic Chemistry[ CHIM.COOR ] Chemical Sciences/Coordination chemistrySonogashira couplingchemistry.chemical_element010402 general chemistry01 natural sciencesMedicinal chemistryCopperCoupling reaction0104 chemical sciencesCatalysisInorganic Chemistrychemistry.chemical_compoundchemistryPhenylacetyleneMolecule[CHIM.COOR]Chemical Sciences/Coordination chemistryPhysical and Theoretical ChemistryComputingMilieux_MISCELLANEOUSPalladium
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Cover Picture: Selective Synthesis of Partially Protected Nonsymmetric Biphenols by Reagent‐ and Metal‐Free Anodic Cross‐Coupling Reaction (Angew. Ch…

2016

010405 organic chemistryChemistryINTGeneral Chemistry010402 general chemistryElectrochemistry01 natural sciencesCatalysisCoupling reaction0104 chemical sciencesAnodeC c couplingMetal freeReagentPolymer chemistryOrganic chemistryCover (algebra)Angewandte Chemie International Edition
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Photoswitching of the antiferromagnetic coupling in an oxamato-based dicopper(ii) anthracenophane

2011

Thermally reversible photomagnetic (ON/OFF) switching behavior has been observed in a dinuclear oxamatocopper(ii) anthracenophane upon UV light irradiation and heating; the two CuII ions (SCu = 1/2) that are antiferromagnetically coupled in the dicopper(ii) metallacyclic precursor (ON state) become uncoupled in the corresponding [4+4] photocycloaddition product (OFF state), as substantiated from both experimental and theoretical studies. © 2011 The Royal Society of Chemistry.

010405 organic chemistryChemistryMetals and AlloysLight irradiation[CHIM.MATE]Chemical Sciences/Material chemistryGeneral Chemistry010402 general chemistryPhotochemistry01 natural sciencesCatalysisAntiferromagnetic coupling0104 chemical sciences3. Good healthSurfaces Coatings and FilmsElectronic Optical and Magnetic MaterialsIonCrystallographyMaterials ChemistryCeramics and CompositesChemical Communications
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Facile synthesis of annulated heterocyclic benzo[kl]acridine derivatives via one-pot N–H/C–H coupling

2016

An efficient N–H/C–H one-pot coupling method for the preparation of benzo[kl]acridines has been developed based on palladium-catalyzed domino synthesis. Using commercially available starting materials such as dihalonaphthalenes and diphenylamines, and combining amination with catalysts for C–H activation, up to 95% overall yield can be achieved.

010405 organic chemistryChemistryOrganic ChemistryAcridine derivatives010402 general chemistry01 natural sciencesMedicinal chemistryDomino0104 chemical sciencesCatalysisCoupling (electronics)Yield (chemistry)Organic chemistryAminationOrganic Chemistry Frontiers
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Photocatalytic Giese Addition of 1,4-Dihydroquinoxalin-2-ones to Electron-Poor Alkenes Using Visible Light.

2020

The visible-light photoredox-catalyzed coupling of 1,4-dihydroquinoxalin-2-ones and Michael acceptors was achieved using Ru(bpy)3Cl2 as the photocatalyst and (PhO)2PO2H as an additive. The optimized reaction conditions provide a good yield for the radical conjugate addition products (44 examples) with a wide range of structurally different Michael acceptors. A gram scale reaction using sunlight irradiation is also described. Furthermore, several transformations were carried out with the Giese addition products.

010405 organic chemistryChemistryOrganic ChemistryElectron010402 general chemistryPhotochemistry01 natural sciencesBiochemistryReaccions químiques0104 chemical sciencesCoupling (electronics)PhotocatalysisAminesPhysical and Theoretical ChemistryQuímica orgànicaVisible spectrumOrganic letters
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Selective Formation of 4,4'-Biphenols by Anodic Dehydrogenative Cross- and Homo-Coupling Reaction.

2019

A simple and selective electrochemical synthesis by dehydrogenative coupling of unprotected 2,6- or 2,5-substituted phenols to the desired 4,4'-biphenols is reported. Using electricity as the oxidizing reagent avoids pre-functionalization of the starting materials, since a selective activation of the substrates takes place. Without the necessity for metal-catalysts or the use of stoichiometric reagents it is an economic and environmentally friendly transformation. The elaborated electrochemical protocol leads to a broad variety of the desired 4,4'-biphenols in a very simplified manner compared to classical approaches. This is particular the case for the cross-coupled products.

010405 organic chemistryChemistryOrganic ChemistryGeneral Chemistry010402 general chemistryElectrochemistry01 natural sciencesEnvironmentally friendlyCombinatorial chemistryCatalysisCoupling reaction0104 chemical sciencesAnodeReagentOxidizing agentDehydrogenationStoichiometryChemistry (Weinheim an der Bergstrasse, Germany)
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