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How lewis acids catalyze diels–alder reactions Vermeeren, Pascal Hamlin, Trevor Fernández López, Israel Bickelhaupt, Matthias 547 Química orgánica (Química) 2306 Química Orgánica The Lewis acid(LA)-catalyzed Diels–Alder reaction between isoprene and methyl acrylate was investigated quantum chemically using a combined density functional theory and coupled-cluster theory approach. Computed activation energies systematically decrease as the strength of the LA increases along the series I2 < SnCl4 < TiCl4 < ZnCl2 < BF3 < AlCl3. Emerging from our activation strain and Kohn–Sham molecular orbital bonding analysis was an unprecedented finding, namely that the LAs accelerate the Diels–Alder reaction by a diminished Pauli repulsion between the p-electron systems of the diene and dienophile. Our results oppose the widely accepted view that LAs catalyze the Diels–Alder reaction by enhancing the donor–acceptor [HOMOdiene–LUMOdienophile] interaction and constitute a novel physical mechanism for this indispensable textbook organic reaction. Netherlands Organization for Scientific Research Ministerio de Economía y Competitividad (España) Depto. de Química Orgánica Fac. de Ciencias Químicas TRUE pub 2024-02-21T08:39:15Z 2024-02-21T08:39:15Z 2020 journal article https://hdl.handle.net/20.500.14352/101614 1433-7851 10.1002/anie.201914582 eng CTQ2016-78205-P Vermeeren, Pascal, et al. «How Lewis Acids Catalyze Diels–Alder Reactions». Angewandte Chemie International Edition, vol. 59, n.o 15, abril de 2020, pp. 6201-06. https://doi.org/10.1002/anie.201914582. Attribution-NonCommercial-NoDerivatives 4.0 International http://creativecommons.org/licenses/by-nc-nd/4.0/ open access application/pdf Wiley