Conformer-specific polar cycloaddition of dibromobutadiene with trapped propene ions

Kilaj, Ardita and Wang, Jia and Stranak, Patrik and Schwilk, Max and Rivero, Uxia and Xu, Lei and von Lilienfeld, O. Anatole and Kupper, Jochen and Willitsch, Stefan. (2021) Conformer-specific polar cycloaddition of dibromobutadiene with trapped propene ions. Nature Communications, 12 (1). p. 6047.

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Identifying a concerted or stepwise mechanism in Diels-Alder reactions is experimentally challenging. Here the authors demonstrate the coexistence of both mechanisms in the reaction of 2,3-dibromobuta-1,3-diene with propene ions, using a conformationally controlled molecular beam reacting with trapped ions and ab initio computations
Diels-Alder cycloadditions are efficient routes for the synthesis of cyclic organic compounds. There has been a long-standing discussion whether these reactions proceed via stepwise or concerted mechanisms. Here, we adopt an experimental approach to explore the mechanism of the model polar cycloaddition of 2,3-dibromo-1,3-butadiene with propene ions by probing its conformational specificities in the entrance channel under single-collision conditions in the gas phase. Combining a conformationally controlled molecular beam with trapped ions, we find that both conformers of the diene, gauche and s-trans, are reactive with capture-limited reaction rates. Aided by quantum-chemical and quantum-capture calculations, this finding is rationalised by a simultaneous competition of concerted and stepwise reaction pathways, revealing an interesting mechanistic borderline case.
Faculties and Departments:05 Faculty of Science > Departement Chemie > Chemie > Chemische Physik (Willitsch)
05 Faculty of Science > Departement Chemie > Former Organization Units Chemistry > Physikalische Chemie (Lilienfeld)
UniBasel Contributors:Kilaj, Ardita and Stranak, Patrik and Rivero Gonzalez, Uxia Constanza and Xu, Lei and Willitsch, Stefan and Schwilk, Max Michael Aaron and von Lilienfeld, Anatole
Item Type:Article, refereed
Article Subtype:Research Article
Publisher:Nature Publishing Group
Note:Publication type according to Uni Basel Research Database: Journal article
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Last Modified:18 Jan 2022 15:42
Deposited On:18 Jan 2022 15:42

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