The effect of the C5-substituent on regioselectivity in the Rh(i)-catalyzed intermolecular transannulation of 1,2,3-thiadiazoles with phenylacetylene

Marina A. Tokareva, Indrek Pernik, Barbara A. Messerle, Tatiana V. Glukhareva, Sinead T. Keaveney*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

5 Citations (Scopus)

Abstract

Despite the growing use of denitrogenative reactions of 1,2,3-thiadiazoles in heterocycle synthesis, the origin of the varied reactivity and divergent regioselectivity observed in their transannulation reactions is not well understood. To address this limitation, systematic studies on the reactivity and regioselectivity in the Rh(i)-catalyzed intermolecular transannulation between a range of substituted 1,2,3-thiadiazoles and phenylacetylene have been conducted. Our experimental data revealed that the electronic nature of the C5-substituent on the 1,2,3-thiadiazole ring influenced reactivity significantly. Moreover, the nature of the substituent was shown to have a remarkable effect on the regioselectivity of the reaction, with electron-donating groups leading to 2,3,4-substituted thiophenes and strong electron-withdrawing groups favouring the 2,3,5-substituted products. Identified experimental trends have been supported and rationalized using density functional theory calculations.

Original languageEnglish
Pages (from-to)2772-2782
Number of pages11
JournalCatalysis Science and Technology
Volume13
Issue number9
Early online date3 Apr 2023
DOIs
Publication statusPublished - 7 May 2023

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