RT Journal Article
T1 How lewis acids catalyze diels–alder reactions
A1 Vermeeren, Pascal
A1 Hamlin, Trevor
A1 Fernández López, Israel
A1 Bickelhaupt, Matthias
AB 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.
PB Wiley
SN 1433-7851
YR 2020
FD 2020
LK https://hdl.handle.net/20.500.14352/101614
UL https://hdl.handle.net/20.500.14352/101614
LA eng
NO 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.
NO Netherlands Organization for Scientific Research
NO Ministerio de Economía y Competitividad (España)
DS Docta Complutense
RD 25 dic 2025