Lewis Acid‐Catalyzed Diels‐Alder Reactions: Reactivity Trends across the Periodic Table

The catalytic effect of various weakly interacting Lewis acids (LAs) across the periodic table, based on hydrogen (Group 1), pnictogen (Group 15), chalcogen (Group 16), and halogen (Group 17) bonds, on the Diels‐Alder cycloaddition reaction between 1,3‐butadiene and methyl acrylate was studied quantum chemically by using relativistic density functional theory. Weakly interacting LAs accelerate the Diels‐Alder reaction by lowering the reaction barrier up to 3 kcal mol(−1) compared to the uncatalyzed reaction. The reaction barriers systematically increase from halogen<hydrogen<chalcogen<pnictogen‐bonded LAs, i. e., the latter have the least catalytic effect. Our detailed activation strain and Kohn‐Sham molecular orbital analyses reveal that these LAs lower the Diels‐Alder reaction barrier by increasing the asynchronicity of the reaction to relieve the otherwise destabilizing Pauli repulsion between the closed‐shell filled π‐orbitals of diene and dienophile. Notably, the reactivity can be further enhanced on going from a Period 3 to a Period 5 LA, as these species amplify the asynchronicity of the Diels‐Alder reaction due to a stronger binding to the dienophile. These findings again demonstrate the generality of the Pauli repulsion‐lowering catalysis concept.