How Lewis Acids Catalyze Ene Reactions

Abstract

The catalytic effect of various Lewis acids (LAs) on the ene reaction between propene (ene) and but-3-en-2-one (enophile) was studied quantum chemically using density functional theory and with coupled-cluster theory. The studied LAs efficiently accelerate the ene reaction by lowering the reaction barrier up to 12 kcal mol−1 compared to the uncatalyzed reaction. Our detailed activation strain and Kohn-Sham molecular orbital analyses reveal that coordination of a LA catalyst to the enophile decreases the reaction barrier of the ene reaction by inducing an asymmetry in the π-electronic system, which increases the asynchronicity and hence relieves the otherwise highly destabilizing activation strain and Pauli repulsion between the closed-shell filled π-orbitals of the ene and enophile. In all, these findings further demonstrate the generality of the Pauli-lowering catalysis concept.