TY  - EJOUR
AU  - Kilaj, Ardita
AU  - Wang, Jia
AU  - Straňák, Patrik
AU  - Schwilk, Max
AU  - Rivero, Uxía
AU  - Xu, Lei
AU  - von Lilienfeld, O. Anatole
AU  - Küpper, Jochen
AU  - Willitsch, Stefan
TI  - Conformer-specific polar cycloaddition of dibromobutadiene with trapped propene ions
IS  - arXiv:2107.13858
M1  - PUBDB-2024-01849
M1  - arXiv:2107.13858
PY  - 2021
AB  - 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 a new experimental approach to explore the mechanistic details 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.
LB  - PUB:(DE-HGF)25
DO  - DOI:10.3204/PUBDB-2024-01849
UR  - https://bib-pubdb1.desy.de/record/607360
ER  -