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Meisenheimer complexes as hidden intermediates in the aza-S_NAr mechanism

Ormazábal-Toledo, Rodrigo and Richter, Sebastián and Robles-Navarro, Andrés and Maulén, Boris and Matute, Ricardo A. and Gallardo-Fuentes, Sebastián (2020) Meisenheimer complexes as hidden intermediates in the aza-S_NAr mechanism. Organic and Biomolecular Chemistry, 18 (22). pp. 4238-4247. ISSN 1477-0520. https://resolver.caltech.edu/CaltechAUTHORS:20200520-145238610

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Abstract

In this work we report a computational study about the aza-S_NAr mechanism in fluorine- and chlorine-containing azines with the aim to unravel the physical factors that determine the reactivity patterns in these heterocycles towards propylamine. The nature of the reaction intermediate was analyzed in terms of its electronic structure based on a topological analysis framework in some non-stationary points along the reaction coordinate. The mechanistic dichotomy of a concerted or a stepwise pathway is interpreted in terms of the qualitative Diabatic Model of Intermediate Stabilization (DMIS) approach, providing a general mechanistic picture for the S_NAr process involving both activated benzenes and nitrogen-containing heterocycles. With the information collected, a unified vision of the Meisenheimer complexes as transition state, hidden intermediate or real intermediate was proposed.


Item Type:Article
Related URLs:
URLURL TypeDescription
https://doi.org/10.1039/d0ob00600aDOIArticle
http://www.rsc.org/suppdata/d0/ob/d0ob00600a/d0ob00600a1.pdfPublisherSupplementary Information
ORCID:
AuthorORCID
Ormazábal-Toledo, Rodrigo0000-0003-1777-0426
Matute, Ricardo A.0000-0002-0644-3799
Additional Information:© 2020 The Royal Society of Chemistry. Submitted 22 Mar 2020; Accepted 18 May 2020; First published 18 May 2020. The authors thank to FONDECYT of Chile for project grants Regular 1160061 and 1181260 and Postdoctoral Fellow 3170653. Powered@NLHPC: This research was partially supported by the supercomputing infrastructure of the NLHPC (ECM-02). There are no conflicts to declare.
Funders:
Funding AgencyGrant Number
Fondo Nacional de Desarrollo Científico y Tecnológico (FONDECYT)1160061
Fondo Nacional de Desarrollo Científico y Tecnológico (FONDECYT)1181260
Fondo Nacional de Desarrollo Científico y Tecnológico (FONDECYT)3170653
Laboratorio Nacional de Computación de Alto RendimientoECM-02
Issue or Number:22
Record Number:CaltechAUTHORS:20200520-145238610
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20200520-145238610
Official Citation:Meisenheimer complexes as hidden intermediates in the aza-S_NAr mechanism. Org. Biomol. Chem., 2020, 18, 4238-4247; doi: 10.1039/d0ob00600a
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:103368
Collection:CaltechAUTHORS
Deposited By: Tony Diaz
Deposited On:20 May 2020 22:03
Last Modified:11 Jun 2020 18:27

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