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...

For the first time the unimolecular Newman–Kwart rearrangement is performed in pure water. The elevated temperatures required for the 1,3-aryl shift are easily accomplished by microwave irradiation. Differently functionalized substrates underline the expected influence on the reaction rate regarding the electronic and steric effects of the substituents. The utilization of supramolecular additiv...

In order to find the susceptibility of the Claisen rearrangement and next proton shift reaction of ally) aryl etherto the substiment effects in pan position, the kinetic and the:rmodynamie parameters are calculated at The33 LTP level using 6-3110. b asis set. The calculated activation energies for the rearrangements and protonshift reactions are around 3133 kcaUmol and 52.16 kcal/mol, nap.. liv...

A unified synthetic strategy toward caged Garcinia natural products has been designed and implemented. Central to the strategy is a tandem Claisen/Diels-Alder/Claisen rearrangement of a suitably substituted xanthone precursor to form forbesione (1a). Serving as a template, forbesione is then used to deliver representative members of this family, including desoxygaudichaudione A (4), desoxymorel...

An amorphous selenium network structure was constructed by combination of a lattice random walk and ab initio molecular dynamic (MD) simulation. The static structure factor, pair correlation function, and vibrational and electronic density of states simultaneously agree with experiment. For the first time, we study structural rearrangement due to light-induced changes in occupation. The predict...

The Hock rearrangement is an acid catalyzed reaction involving organic hydroperoxides and resulting in oxidative cleavage of adjacent C–C bonds. It has significant industrial applications, like the production phenol (cumene process), but it remains scarcely used synthesis. In addition, its detailed mechanism never been studied. Thus, we report herein a theoretical study rearrangement, using InC...

We illustrate how the electronic charge reconstruction near the interfaces of metal–strongly-correlatedbarrier–metal devices can lead to a significant enhancement of the thermoelectric response due to the breaking of particle-hole symmetry. We show how one can achieve effective Seebeck coefficients larger than 150 μV/K and effective electronic figures-of-merit ZT higher than 1. Our work shows t...

Vinyl cyclopropane rearrangement (VCPR) has been utilised to synthesise a difluorinated cyclopentene stereospecifically and under mild thermal conditions. Difluorocyclopropanation chemistry afforded ethyl 3-(1'(2'2'-difluoro-3'-phenyl)cyclopropyl) propenoate as all four stereoisomers (18a, 18b, 22a, 22b) (all racemic). The trans-E isomer (18a), prepared in 70 % yield over three steps, underwent...

objective: group a rotaviruses (garv) are responsible for the vast majority of severe diarrhea worldwide that kills an estimated 600,000-870,000 children annually. since infantile gastroenteritis is a main health problem, therefore diagnosis and treatment of this disease is crucial. gene rearrangements have been detected in vitro during serial passages of the virus at a high multiplicity of inf...

High harmonic generation (HHG) spectroscopy has opened up a new frontier in ultrafast science, where electronic dynamics can be measured on an attosecond time scale. The strong laser field that triggers the high harmonic response also opens multiple quantum pathways for multielectron dynamics in molecules, resulting in a complex process of multielectron rearrangement during ionization. Using co...