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...

Thermal rearrangement of 2-thiabicyclo[ 3.2.0]hepta-3,6-diene-6,7-dicarbonitriles 1-3 to their 4,5-dicarbonitrile isomers 4-6 takes place at 110-140 "C in yields of 82-84%. The reactions are first order with rates almost independent of the polarity of the solvent. Activation parameters (m = 120-140 kJ mol-' and AS* = 0 J K-l mol-') are in agreement with a concerted symmetry-allowed antarafacial...

Steric effect is used to obtain a highly diastereoselective rearrangement reaction.

Rearrangement reactions of cycloalkenyl phenol and naphthyl ethers and the acid-catalyzed cyclization of the resulting product were investigated. Claisen rearrangement afforded 2-substituted phenol and naphthol derivatives. Combined Claisen and Cope rearrangement resulted in the formation of 4-substituted phenol and naphthol derivatives. In the case of cycloocthylphenyl ether the consecutive Cl...

The synthesis of a homologous series of transoid, bridged sym-oxepin oxides (loa-c) is described. The lower homologues, IOa,b, do not undergo facile Cope rearrangement to the sym-oxepin oxides 15a,b. The generation of transoid 1Oc led rapidly to the production of the Cope rearrangement product 15c. The differing reactivity in the series loa-c is attributed to the inability of lOa,b to interconv...

As the basis and preliminary work of future experimental study on PAHs formation under high temperature, theoretical computations on the intramolecular rearrangement reactions of sylvestrene (1-methyl-3-vinylcyclohexene) and 1,4-dimethyl-4-vinylcyclohexene are conducted and reveal that they may be transformed to themselves. The conversion between Dipentene and 2,4-dimethyl-4-vinylcyclohexen...