Möbius‐Aromaticity and Antiaromaticity Driven Nucleophilic Substitution Reactions in Cycloheptatrienide Zwitterions with a Twisted Cycloheptatetraene Intermediate

Möbius‐Aromaticity and Antiaromaticity Driven Nucleophilic Substitution Reactions in Cycloheptatrienide Zwitterions with a Twisted Cycloheptatetraene Intermediate Научная публикация

Журнал

Asian Journal of Organic Chemistry
ISSN: 2193-5815 , E-ISSN: 2193-5807

Вых. Данные

Год: 2025, Номер статьи : e202500119, Страниц : DOI: 10.1002/ajoc.202500119

Авторы

Salikov Rinat F. ¹ , Sokolova Alena D. ¹ , Platonov Dmitry N. ¹ , Belyy Alexander Yu. ¹ , Khitrov Michael D. ^1,2 , Tomilov Yury V. ¹

Организации

1	FSBIS N D Zelinsky Institute of Organic Chemistry of the Russian Academy of Sciences: FGBUN Institut organiceskoj himii imeni N D Zelinskogo Rossijskoj akademii nauk Laboratory of Diazocompound Chemistry 47 Leninsky Prospect 119991 Moscow RUSSIAN FEDERATION
2	Department of Chemistry, Moscow State University, 119992 Moscow, Russian Federation

Pyridinium and phosphonium zwitterions featuring a cycloheptatrienide-anion moiety are introduced into antiaromatic nucleophilic substitution reactions. The transformations afford other zwitterions, cycloheptatrienes or cycloheptatrienide salts. The initial reaction stage involves an elimination of pyridine or triphenylphosphine to form a Möbius-aromatic cycloheptatetraene intermediate. The aromatic stabilization energy in parent cycloheptatetraene was estimated at 6–7 kcal/mol, an important value in terms of reaction rates. An anisotropy of the induced current density diagram illustrated the diatropic ring current confirming the aromaticity of the intermediate and an analysis of NICS values for the initial reaction step revealed a transition from a slightly antiaromatic to a moderately aromatic species. Therefore, these reactions are uniquely driven by both the relief of antiaromaticity and the acquisition of Möbius aromaticity.

Salikov R.F. , Sokolova A.D. , Platonov D.N. , Belyy A.Y. , Khitrov M.D. , Tomilov Y.V.
Möbius‐Aromaticity and Antiaromaticity Driven Nucleophilic Substitution Reactions in Cycloheptatrienide Zwitterions with a Twisted Cycloheptatetraene Intermediate
Asian Journal of Organic Chemistry. 2025. e202500119 . DOI: 10.1002/ajoc.202500119 WOS Scopus OpenAlex

Web of science:	WOS:001443611300001
Scopus:	2-s2.0-86000640586
OpenAlex:	W4408331088

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