Meshalkin, Stepan A. and Tsybulin, Semyon V. and Bardakov, Victor G. and Tatarinov, Ilya A. and Shitov, Daniil A. and Tupikina, Elena Y. and Efremova, Mariia M. and Antonov, Alexander S. (2024) Buttressing Effect in the Halogen-Lithium Exchange in ortho-Bromo-N,N-dimethylanilines and Related Naphthalenes. CHEMISTRY-A EUROPEAN JOURNAL, 30 (14). e202303956. ISSN 0947-6539, 1521-3765
Full text not available from this repository. (Request a copy)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 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.
| Item Type: | Article |
|---|---|
| Uncontrolled Keywords: | ORGANOLITHIUM REAGENTS; PROTON SPONGE; DEPROTONATION; REACTIVITY; buttressing effect; halogen-lithium exchange; organolithium; steric strain; aniline |
| Subjects: | 500 Science > 540 Chemistry & allied sciences |
| Divisions: | Chemistry and Pharmacy > Institut für Organische Chemie > Arbeitskreis Prof. Dr. Ruth Gschwind |
| Depositing User: | Dr. Gernot Deinzer |
| Date Deposited: | 14 Jan 2026 05:40 |
| Last Modified: | 14 Jan 2026 05:40 |
| URI: | https://pred.uni-regensburg.de/id/eprint/63897 |
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