The Antiaromatic Nucleophilic Substitution Reaction (SNAAr) in Cycloheptatrienyl-Anion Containing Zwitterions with a Möbius-Aromatic Intermediate

Antiaromatic nucleophilic substitution reactions in cycloheptatrienide pyridinium and phosphonium zwitterions with initial formation of a cycloheptatetraene intermediate are explored. The mechanism was supported by quantum chemical calculations, first-order reaction kinetics, and high-resolution mas...

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Bibliographic Details
Published in:Organic letters 2024-07, Vol.26 (28), p.5877-5882
Main Authors: Sokolova, Alena D., Platonov, Dmitry N., Belyy, Alexander Yu, Salikov, Rinat F., Erokhin, Kirill S., Tomilov, Yury V.
Format: Article
Language:English
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Summary:Antiaromatic nucleophilic substitution reactions in cycloheptatrienide pyridinium and phosphonium zwitterions with initial formation of a cycloheptatetraene intermediate are explored. The mechanism was supported by quantum chemical calculations, first-order reaction kinetics, and high-resolution mass spectrometry. The pyridinium zwitterion exhibited weak antiaromaticity, whereas the intermediate displayed Möbius aromaticity, as evidenced by nuclear independent chemical shift values and the shape of its HOMO. This study represents the eighth confirmed instance of a Möbius-aromatic organic species in its ground state.
ISSN:1523-7060
1523-7052
DOI:10.1021/acs.orglett.4c01446