title: Methyl substituent effects in radical cation Diels-Alder reactions.
abstract: The effect of methyl substitution on the Diels-Alder radical cation reaction was studied using B3LYP with a 6-31G* basis set. Five separate pathways, one concerted and four stepwise, were examined for each possible position of a methyl substituent. None of the concerted transition structures could be located without symmetry constraints, and all but one of the structures obtained under these conditions were destabilized by a second-order Jahn-Teller distortion. A concerted pathway with simultaneous bond formation at C1 and C4 is therefore excluded. Stepwise pathways that had the methyl group either on a carbon involved in the initial bond formation or in a position where it could not stabilize the radical/cation were a few kcal/mol above alternate pathways. High transition state energies for the formation of vinylcyclobutane derivatives cause it to be a minor product in general. The pathway that proceeds through an anti-intermediate is the most favored, while the pathways forming the gauche-out intermediate that converts to the anti-intermediate is also strongly represented. Both of the major pathways lead directly to the formation of the methylcyclohexene product.
authors.affiliation: Department of Chemistry and Biochemistry, University of Notre Dame, Notre Dame, Indiana 46556-5670, USA.
authors.forename: Nicholas A
authors.initials: NA
authors.lastname: Valley
authors.forename: Olaf
authors.initials: O
authors.lastname: Wiest