Hetero-Diels–Alder reactions involving Fe(CO)3-coordinated dienal and formyltrimethylenemethane catalyzed by Lewis acids — A theoretical study

Abstract

The hetero-Diels–Alder reactions of butadiene with Fe(CO)3-coordinated formylbutadiene and formyltrimethylenemethane catalyzed by Lewis acids have been theoretically studied through density functional calculations. The results obtained show that, for the reaction with (formylbutadiene)Fe(CO)3, the kinetically most favourable product is the one corresponding to the attack of butadiene on the s-cis conformer of the formylbutadiene fragment when the reaction is catalyzed by BF3, and the one corresponding to the attack on the s-trans conformer when the catalyst is TiCl4. On the other hand, for the reaction with (formyltrimethylenemethane)Fe(CO)3 catalyzed by BF3, the product corresponding to the attack on the s-trans conformer is predicted to be favoured. These results have been interpreted through an energy decomposition analysis of the potential-energy barriers.