23° SEMINARIO QUÍMICA ORGÁNICA IQUIR 2022

SEMINARIO QUÍMICA ORGÁNICA 17-10-22

EXPOSITOR: Dr. Iván Cortés

TÍTULO: "Origin of Catalysis and Selectivity in Lewis Acid-Promoted Diels− Alder Reactions Involving Vinylazaarenes as Dienophiles".

FUENTE: Susana Portela and Israel Fernández.

J. Org. Chem. 2022, 87, 9307−9315, DOI: https://doi.org/10.1021/acs.joc.2c01035.
Chem. Sci., 2021, 12, 15947−15952, DOI: https://doi.org/10.1039/D1SC05095H.

DÍA, HORA y LUGAR: Lunes 17 de octubre de 2022, 14:00 h, Aula 18 FBIOYF. 

Modalidad virtual, Link: meet.google.com/hjn-ygro-twf (Plataforma MEET GOOGLE)

RESUMEN: 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 that the 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.