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Hole Catalysis of Cycloaddition Reactions: How to Activate and Control Oxidant Upconversion in Radical-Cationic Diels-Alder Reactions.
J Am Chem Soc
September 2023
Department of Chemistry and Biochemistry, Florida State University, Tallahassee, Florida 32306, United States.
In order to use holes as catalysts, the oxidized product should be able to transfer the hole to a fresh reactant. For that, the hole-catalyzed reaction must increase the oxidation potential along the reaction path, i.e.
View Article and Find Full Text PDFFactors Governing Reactivity and Selectivity in Hydrogen Atom Transfer from C(sp)-H Bonds of Nitrogen-Containing Heterocycles to the Cumyloxyl Radical.
J Org Chem
June 2022
Dipartimento di Scienze e Tecnologie Chimiche, Università"Tor Vergata", Via Della Ricerca Scientifica, 1, Rome I-00133, Italy.
A kinetic study of the hydrogen atom transfer (HAT) reactions from nitrogen-containing heterocycles (secondary and tertiary lactams, 2-imidazolidinones, 2-oxazolidinones, and succinimides) to the cumyloxyl radical has been carried out employing laser flash photolysis with ns time resolution. HAT occurs from the C-H bonds that are α to nitrogen, activated by hyperconjugative overlap with the N-C═O π system. In the lactam series, the second-order HAT rate constant () was observed to decrease by a factor of ∼4 going from the five- and six-membered ring derivatives to the eight-membered ones, a behavior that was rationalized on the basis of a reduced extent of hyperconjugative activation associated to the greater flexibility of the larger rings compared to the smaller ones.
View Article and Find Full Text PDFImportance of water and intramolecular interaction governs substantial blue shift of C -H stretching frequency in complexes between chalcogenoaldehydes and water.
RSC Adv
January 2022
Laboratory of Computational Chemistry and Modelling (LCCM), Department of Chemistry, Faculty of Natural Sciences, Quy Nhon University Vietnam
Geometrical structure, stability and cooperativity, and contribution of hydrogen bonds to the stability of complexes between chalcogenoaldehydes and water were thoroughly investigated using quantum chemical methods. The stability of the complexes increases significantly when one or more HO molecules are added to the binary system, whereas it decreases sharply going from O to S, Se, or Te substitution. The O-H⋯O H-bond is twice as stable as C -H⋯O and O-H⋯S/Se/Te H-bonds.
View Article and Find Full Text PDFCorrelation between Optical Activity and the Helical Molecular Orbitals of Allene and Cumulenes.
Org Lett
October 2020
Laboratory for Computational Molecular Design, Institute of Chemical Sciences and Engineering, Ecole Polytechnique Federale de Lausanne (EPFL), 1015 Lausanne, Switzerland.
Helical frontier molecular orbitals (MOs) appear in disubstituted allenes and even- cumulenes. Chiral molecules are optically active, but while these molecules are single-handed chiral, π-orbitals of both helicities are present. Here we computationally examine whether the optical activity of chiral cumulenes is controlled by the axial chirality or the helicity of the electronic structure.
View Article and Find Full Text PDFMedium-Dependent Crossover from the Red to Blue Shift of the Donor's Stretching Fundamental in the Binary Hydrogen-Bonded Complexes of CDCl with Ethers and Ketones.
J Phys Chem A
September 2020
School of Chemical Sciences, Indian Association for the Cultivation of Science, Kolkata 700032, India.
Article Synopsis
- Mid-infrared spectra were measured for hydrogen-bonded complexes of CDCl with different solvents (acetone, cyclohexanone, diethyl ether, and tetrahydrofuran) at room temperature and in a cold argon matrix.
- Notable changes in spectral shift (Δν) were observed, with acetone and cyclohexanone showing a switch from blue shift in vapor to red shift in the matrix, while the ethers had larger red shifts and enhanced transition intensity.
- The differences in spectral behavior were explained by charge transfer interactions at H-bonding sites and changes in H-bond distance, with some complexes showing various substructures in
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