Transition state analysis on regioselectivity in [2+2] photocycloaddition reactions of substituted 2-cyclohexenone with cycloalkenecarboxylates

Abstract

The experimental results of the triplet [2+2] photocycloaddition reactions of substituted 2-cyclohexenone 1 with cycloalkenylesters 2 , 3 , 4 have showed remarkable change in the regioselectivity of the products. The ht/hh product ratio increases with increment of the cycle-size. The FMO investigations in addition to the transition state analysis were used to rationalize such regioselectivity. The FMO method with their orbital coefficients and energies could not explain the reaction selectivity since these values of 2– 4 showed tendency to form the hh adduct mainly. PM3, PM5, CIS/6-31G, and B3LYP/6-31G methods were used to locate the hh and ht transition states of the three reactions. As the potential energy barriers (TS1) on the first TS surface for the major products were lower than that for the minor products in most of the cases, the real ratio can be explained in terms of TS analysis. The recently improved PM5 and the B3LYP methods were more successful in this debate as partitioning the activation energy at the potential energy barriers into reactant deformation and the interaction (or repulsion) energies is easy and effective. The changes in the ht/hh ratio with the enlargement of the alkene ring size may be due to the increment of the repulsion energy and large changes in the deformation energy of the reactants. In the transition state structures the stabilities of the major products are thought to be due to the existence of some repulsion between the enone carbonyl and esters in the alkenylesters, and some hydrogen bonding between the reactants. The FMO and second transition state (TS2) energy on the biradical intermediates are also thought to play some role in controlling the product selectivity by lowering the closure energy of the biradicals according to the possibility of their overlapping.