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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. and Antonov, Alexander S. (2023) “Buttressing Effect” in the Halogen‐Lithium Exchange in ortho‐Bromo‐N,N‐dimethylanilines and Related Naphthalenes. Chemistry – A European Journal.

Date of publication of this fulltext: 18 Jan 2024 06:40
Article
DOI to cite this document: 10.5283/epub.55345


Abstract

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.



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Details

Item typeArticle
Journal or Publication TitleChemistry – A European Journal
Publisher:Wiley
Date22 December 2023
InstitutionsChemistry and Pharmacy > Institut für Organische Chemie
Identification Number
ValueType
10.1002/chem.202303956DOI
Keywordsbuttressing effect · halogen-lithium exchange · organolithium · steric strain · aniline
Dewey Decimal Classification500 Science > 540 Chemistry & allied sciences
StatusPublished
RefereedYes, this version has been refereed
Created at the University of RegensburgPartially
URN of the UB Regensburgurn:nbn:de:bvb:355-epub-553450
Item ID55345

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