Regio- and sterochemistry of the [2+2]-cycloaddition reaction between enones and alkenes. A DFT study

Abstract

Calculations at DFT/B3LYP/6-31G+(d,p) level of theory have been performed on the photochemical interaction between enones and alkenes. The photochemical reaction of cyclopentenone with ethyl vinyl ether can be explained assuming the reaction occurs through the triplet excited state of the enone. The interaction between the LSOMO of triplet cyclopentenone and the HOMO of ethyl vinyl ether accounts for the observed stereochemistry. The same behaviour has been observed in the reaction of 3-methylcyclohexenone with 1,1-dimethoxyethene, vinyl acetate, and allene. In the reaction of 3,5,5-trimethylcyclohexenone with methyl cyclobutene-1-carboxylate, the observed regiochemistry can be explained assuming a sensitized reaction able to populate the triplet state of methyl cyclobutene-1-carboxylate. The coupling of the HSOMO of this species with the LUMO of the cyclohexenone derivative account for the observed regiochemistry. Furthermore, the coupling of the radical carbon atoms on the biradical intermediate accounts for the observed stereochemistry. In the reaction of 3-methylcyclohexenone with methyl cyclohexene-1-carboxylate the coupling between the LSOMO of triplet state of 3-methylcyclohexenone and the HOMO of the alkene gave two possible biradical intermediates. The most stable one accounts for the observed regiochemistry. The coupling of the radical carbon atom on the HSOMO and LSOMO of the biradical intermediate accounts for the observed stereochemistry. The coupling between the LSOMO of the triplet state of 3-phenylcyclohexenone and the HOMO of cyclopentene accounts for the observed regiochemistry. The stereochemistry can be explained considering the coupling of the LSOMO and HSOMO in the biradical intermediate.