Through-Space, Lone-Pair Promoted Aromatic Substitution: A Relay Mechanism Can Beat Out Direct Activation.
density functional theory
electrophilic substitution
fluorine
noncovalent interactions
pre-complexation
Journal
Chemistry (Weinheim an der Bergstrasse, Germany)
ISSN: 1521-3765
Titre abrégé: Chemistry
Pays: Germany
ID NLM: 9513783
Informations de publication
Date de publication:
15 Sep 2023
15 Sep 2023
Historique:
received:
17
05
2023
medline:
23
5
2023
pubmed:
23
5
2023
entrez:
23
5
2023
Statut:
ppublish
Résumé
We report a detailed experimental and theoretical analysis of through-space arene activation with halogens, tetrazoles and achiral esters and amides. Contrary to previously assumed direct activation through σ-complex stabilization, our results suggest that these reactions proceed by a relay mechanism wherein the lone pair-containing activators form exothermic π-complexes with electrophilic nitronium ion before transferring it to the probe ring through low barrier transition states. Noncovalent interactions (NCI) plots and Quantum Theory of Atoms in Molecules (QTAIM) analyses depict favorable interactions between the Lewis base (LB) and the nitronium ion in the precomplexes and the transition states, suggesting directing group participation throughout the mechanism. The regioselectivity of substitution also comports with a relay mechanism. In all, these data pave the way for an alternate platform of electrophilic aromatic substitution (EAS) reactions.
Identifiants
pubmed: 37219499
doi: 10.1002/chem.202301550
doi:
Types de publication
Journal Article
Langues
eng
Sous-ensembles de citation
IM
Pagination
e202301550Subventions
Organisme : National Science Foundation
ID : CHE 2102116
Organisme : National Science Foundation
ID : CHE 1856416
Organisme : Natural Sciences and Engineering Research Council of Canada
ID : RGPIN-2019-04205
Informations de copyright
© 2023 The Authors. Chemistry - A European Journal published by Wiley-VCH GmbH.
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