a theoretical study of the kinetic and mechanism of 3-aug-cope rearrangement in gas phase was performed usingdet methods at b3lyp levels of theory with 6-3114ig(d,p) bass set at 298.i5k. equilibrium moleculargeometries and harmonic vibrational frequencies of the reactant, transition state did product were calculated. then,rate constant and activation thermodynamics parameters were calculated an...

The combination of palladium catalysis and thermal cycloaddition is shown to transform tricyclic aziridines into complex, stereodefined tetracyclic products in a single step. This highly unusual cascade process involves diverted Tsuji–Trost sequence leading surprisingly facile intramolecular Diels–Alder reaction. starting materials are accessible on multigram scales from the photochemical rearr...

The 2-Aza-Cope rearrangement of γ-alkenyl nitrones is a rare example of the neutral thermal 2-aza-Cope process that usually takes place with cationic species. During the rearrangement, a redistribution of bonds and electronic density occurs in one kinetic step. However, the introduction of substituents with different steric requirements and electronic features might alter the activation energie...

In an approach to the biologically important 6-azabicyclo[3.2.1]octane ring system, the scope of the tandem 4-exo-trig carbamoyl radical cyclization-dithiocarbamate group transfer reaction to ring-fused β-lactams is evaluated. β-Lactams fused to five-, six-, and seven-membered rings are prepared in good to excellent yield, and with moderate to complete control at the newly formed dithiocarbamat...

Extensive Molecular Dynamics simulations have been performed to investigate the structural and thermal properties of Si-doped fullerenes containing one and two silicon atoms. Both, a many-body potential and ab initio Density Functional Theory ~DFT! have been used to investigate the structural features of the heterofullerenes. The competition between the exohedral and the substitutional types of...

Furanosesquiterpenoids, abundantly available in secondary plant metabolites show inspiring biological activities and some of them are utilized as pharmaceuticals. The aim of the present study was structural elucidation and stereochemical assignments of furanosesquiterpenoids form a new source viz. Himalayan Lauraceae. Compounds 15 were isolated from the essential oils of two Lauraceae species a...

The thermal stability of photo-imprinted Bragg gratings formed in reactiveatmosphere, RF-magnetron sputtered germanosilicate thin films was evaluated in terms of point defect modifications observed during isochronal annealing. Optical and magnetic spectroscopes were utilized to evaluate structural relaxation in these sputtered glasses on both a local and medium-range size scale. Depending upon ...