6533b827fe1ef96bd1285abd

RESEARCH PRODUCT

A DFT study of the mechanism of Brønsted acid catalysed Povarov reactions

Mar Ríos-gutiérrezLuis R. DomingoHatem Layeb

subject

ChemistryOrganic ChemistryImineRegioselectivityProtonationPhotochemistryMethylenecyclopropaneBiochemistryMedicinal chemistrychemistry.chemical_compoundNucleophileDrug DiscoveryElectrophilePovarov reactionBrønsted–Lowry acid–base theory

description

Abstract The molecular mechanism of the Bronsted acid (BA) catalysed Povarov reaction of N -phenyl- C -methoxycarbonyl imine with a methylenecyclopropane (MCP) has been investigated using DFT methods at the MPWB1K/6-31G(d) level. This BA catalysed Povarov reaction is a domino process initialised by the formation of a cationic intermediate which experiences a quick intramolecular Friedel–Crafts reaction yielding the final tetrahydroquinoline. Protonation of the imine nitrogen atom notably increases the electrophilicity of the corresponding species, accelerating the reaction through ionic processes. Analysis of the Parr functions in the initial nucleophilic attack of MCP to the protonated imine allows explaining the total regioselectivity experimentally observed. An electron localisation function quantum topological analysis of the bonding changes along the BA catalysed Povarov reaction permits a complete characterisation of the molecular mechanism.

yearjournalcountryeditionlanguage
2015-12-01Tetrahedron
https://doi.org/10.1016/j.tet.2015.10.012