Computational study of the rate constants and free energies of intramolecular radical addition to substituted anilines.

ABSTRACT: The intramolecular radical addition to aniline derivatives was investigated by DFT calculations. The computational methods were benchmarked by comparing the calculated values of the rate constant for the 5-exo cyclization of the hexenyl radical with the experimental values. The dispersion-corrected PW6B95-D3 functional provided very good results with deviations for the free activation barrier compared to the experimental values of only about 0.5 kcal mol(-1) and was therefore employed in further calculations. Corrections for intramolecular London dispersion and solvation effects in the quantum chemical treatment are essential to obtain consistent and accurate theoretical data. For the investigated radical addition reaction it turned out that the polarity of the molecules is important and t

SUBMITTER: Gansauer A 

PROVIDER: S-EPMC3778327 | biostudies-literature | 2013

REPOSITORIES: biostudies-literature