The Antiaromatic Nucleophilic Substitution Reaction (S N AAr) in Cycloheptatrienyl-Anion Containing Zwitterions with a Möbius-Aromatic Intermediate.

Autor:	Sokolova AD; N. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, 47 Leninsky prosp., 119991 Moscow, Russian Federation., Platonov DN; N. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, 47 Leninsky prosp., 119991 Moscow, Russian Federation., Belyy AY; N. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, 47 Leninsky prosp., 119991 Moscow, Russian Federation., Salikov RF; N. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, 47 Leninsky prosp., 119991 Moscow, Russian Federation., Erokhin KS; N. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, 47 Leninsky prosp., 119991 Moscow, Russian Federation., Tomilov YV; N. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, 47 Leninsky prosp., 119991 Moscow, Russian Federation.
Jazyk:	angličtina
Zdroj:	Organic letters [Org Lett] 2024 Jul 19; Vol. 26 (28), pp. 5877-5882. Date of Electronic Publication: 2024 Jul 03.
DOI:	10.1021/acs.orglett.4c01446
Abstrakt:	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.
Databáze:	MEDLINE
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