Abstract
DFT (U)B3LYP and (U)M06-2X calculations with 6-31G(d,p) basis sets have been carried out to investigate the influences of the substituents on the regio- and stereo selectivities for the intermolecular [2+2] radical cation cycloaddition reactions between an aliphatic cyclic enol ether and olefins. Four possible pathways for each reaction were explored. The advantageous pathways of the cycloadditions were certified by the free energy barriers and reaction free energies. The structural features which lead to the products with regio- and stereoselectivities were uncovered. The computational results indicated that there are two different mechanisms for these cycloaddition reactions. One is a stepwise mechanism with two transition states along the reaction path while the other is a concerted mechanism with only one transition state. The stepwise mechanism has a much lower barrier. The factors affecting the cycloaddition mechanism have been discussed.
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