Please use this identifier to cite or link to this item:
http://hdl.handle.net/2445/194940
Title: | Computational study of the stability of pyrrolidine-derived iminium ions: exchange equilibria between iminium ions and carbonyl compounds |
Author: | Costa i Arnau, Anna M. Cascales Jiménez, Victor Castro Álvarez, Alejandro Vilarrasa i Llorens, Jaume |
Keywords: | Energia Ions Energy Ions |
Issue Date: | 26-May-2022 |
Publisher: | American Chemical Society |
Abstract: | The tendency of carbonyl compounds to form iminium ions by reaction with pyrrolidine or chiral pyrrolidine derivatives (in other words, the relative stability to hydrolysis of these iminium ions) has been computationally examined, mainly using the M06-2X/6-311+G(d,p) method. We have thus obtained the equilibrium positions for R-CH═O + CH2═CH-CH═N+R2* → R-CH═N+R2* + CH2═CH-CH═O reactions and for related exchanges. In these exchanges, there is a transfer of a secondary amine between two carbonyl compounds. Their relative energies may be used to predict which iminium species can be predominantly formed when two or more carbonyl groups are present in a reaction medium. In the catalytic Michael additions of nucleophiles to iminium ions arising from conjugated enals, dienals, and trienals, if the formation of the new Nu-C bond is favorable, the chances of amino-catalyzed reactions to efficiently proceed, with high conversions, depend on the calculated energy values for these exchange equilibria, where the iminium tetrafluoroborates of the adducts (final iminium intermediates) must be more prone to hydrolysis than the initial iminium tetrafluoroborates. The density functional theory (DFT) calculations indicate that the MacMillan catalysts and related oxazolidinones are especially suitable in this regard. |
Note: | Reproducció del document publicat a: https://doi.org/10.1021/acsomega.1c07020 |
It is part of: | ACS Omega , 2022, vol. 7, num. 22, p. 18247-18258 |
URI: | http://hdl.handle.net/2445/194940 |
ISSN: | 2470-1343 |
Appears in Collections: | Articles publicats en revistes (Química Inorgànica i Orgànica) |
Files in This Item:
File | Description | Size | Format | |
---|---|---|---|---|
731391.pdf | 1.93 MB | Adobe PDF | View/Open |
Items in DSpace are protected by copyright, with all rights reserved, unless otherwise indicated.