Direkt zum Inhalt

Meshalkin, Stepan A. ; Tsybulin, Semyon V. ; Bardakov, Victor G. ; Tatarinov, Ilya A. ; Shitov, Daniil A. ; Tupikina, Elena Y. ; Efremova, Mariia M. ; Antonov, Alexander S.

“Buttressing Effect” in the Halogen‐Lithium Exchange in ortho‐Bromo‐N,N‐dimethylanilines and Related Naphthalenes

Meshalkin, Stepan A., Tsybulin, Semyon V., Bardakov, Victor G., Tatarinov, Ilya A., Shitov, Daniil A., Tupikina, Elena Y., Efremova, Mariia M. und Antonov, Alexander S. (2023) “Buttressing Effect” in the Halogen‐Lithium Exchange in ortho‐Bromo‐N,N‐dimethylanilines and Related Naphthalenes. Chemistry – A European Journal.

Veröffentlichungsdatum dieses Volltextes: 18 Jan 2024 06:40
Artikel
DOI zum Zitieren dieses Dokuments: 10.5283/epub.55345


Zusammenfassung

Non-covalent interactions such as coordination of an organolithium reagent by a directing group and steric repulsion of substituents strongly affect the halogen-lithium exchange process. Here we present the manifestation of the “buttressing effect” – an indirect interaction between two substituents issued by the presence of a third group – and its influence on the ease and selectivity of the ...

Non-covalent interactions such as coordination of an organolithium reagent by a directing group and steric repulsion of substituents strongly affect the halogen-lithium exchange process. Here we present the manifestation of the “buttressing effect” – an indirect interaction between two substituents issued by the presence of a third group – and its influence on the ease and selectivity of the bromine-lithium exchange and the reactivity of formed aryllithiums. The increase of the size of the “buttressing” substituent strongly affects the conformation of a NMe2 group, forcing it to hinder ortho-bromine and thus slowing down the exchange. In naphthalene substrates bearing two bromines, this suppresses regioselectivity of the reaction. The “buttressing effect” forces formed aryllithiums to deaggregate, thus boosting their reactivity. This facilitates the decomposition via protolisys by ethereal solvents even at low temperatures and in some cases initiates fast Wurtz-Fittig coupling.



Beteiligte Einrichtungen


Details

DokumentenartArtikel
Titel eines Journals oder einer ZeitschriftChemistry – A European Journal
Verlag:Wiley
Datum22 Dezember 2023
InstitutionenChemie und Pharmazie > Institut für Organische Chemie
Identifikationsnummer
WertTyp
10.1002/chem.202303956DOI
Stichwörter / Keywordsbuttressing effect · halogen-lithium exchange · organolithium · steric strain · aniline
Dewey-Dezimal-Klassifikation500 Naturwissenschaften und Mathematik > 540 Chemie
StatusVeröffentlicht
BegutachtetJa, diese Version wurde begutachtet
An der Universität Regensburg entstandenZum Teil
URN der UB Regensburgurn:nbn:de:bvb:355-epub-553450
Dokumenten-ID55345

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