RT Journal Article
T1 Origin of Catalysis and Selectivity in Lewis Acid-Promoted Diels–Alder Reactions Involving Vinylazaarenes as Dienophiles
A1 Portela García de Blas, Susana
A1 Fernández López, Israel
AB The poorly understood factors controlling the catalysis and selectivity in Lewis acid-promoted Diels−Alder cycloaddition reactions involving vinylazaarenes as dienophiles have been quantitatively explored in detail by means of computational methods. With the help of the activation strain model and the energy decomposition analysis methods, it is found thatthe remarkable acceleration induced by the catalysis is mainly due to a significant reduction of the Pauli repulsion between the key occupied π-molecular orbitals of the reactants and not due to the proposed stabilization of the lowest unoccupied molecular orbital (LUMO) of the dienophile. This computational approach has also been helpful to understand the reasons behind the extraordinary regio- and diastereoselectivity observed experimentally. The insight gained in this work allows us to predict even more reactive vinylazaarene dienophiles, which may be useful in organic synthesis.
PB ACS Publications
SN 0022-3263
YR 2022
FD 2022-07-06
LK https://hdl.handle.net/20.500.14352/71865
UL https://hdl.handle.net/20.500.14352/71865
LA eng
NO CRUE-CSIC (Acuerdos Transformativos 2022)
NO Ministerio de Ciencia e Innovación (MICINN)//AEI/ 10.13039/501100011033
DS Docta Complutense
RD 2 may 2024