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Cycloaddition of Butadiene with Perfluoroethylene: Prediction of a Periselectivity Switch under Pressure
Mohammed Loukili1,2, Ivan Rivilla1,3,4, Fernando P Cossio3
1Donostia International Physics Center, Paseo Manuel de Lardizabal 4, 20018 Donostia-San Sebastián, Spain.
Abstract:
Defying the common Diels-Alder reactivity, the thermal cycloaddition between butadiene and tetrafluoroethylene (TFE) yields exclusively a [2 + 2] cycloadduct via a stepwise diradical mechanism. Here, we study the possibility of reverting to the normal [4 + 2] reactivity in this reaction under high pressure. DFT calculations using the eXtreme Pressure Polarizable Continuum Model (XP-PCM) suggest a more negative activation volume for the concerted [4 + 2] mechanism than the stepwise [2 + 2] mechanism and predict a switch in periselectivity at 1.4 gigapascal (GPa).
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