Extraordinary Mechanism of the Diels-Alder Reaction: Investigation of Stereochemistry, Charge Transfer, Charge Polarization, and Biradicaloid Formation

The Journal of Physical Chemistry. a
Thomas SextonDieter Cremer

Abstract

The Diels-Alder reaction between 1,3-butadiene and ethene is investigated from far-out in the entrance channel to the very last step in the exit channel thus passing two bifurcation points and extending the range of the reaction valley studied with URVA (Unified Reaction Valley Approach) by 300% compared to previous studies. For the first time, the pre- and postchemical steps of the reaction are analyzed at the same level of theory as the actual chemical processes utilizing the path curvature and its decomposition into internal coordinate or curvilinear coordinate components. A first smaller charge transfer to the dienophile facilitates the rotation of gauche butadiene into its cis form. The actual chemical processes are initiated by a second larger charge transfer to the dienophile that facilitates pyramidalization of the reacting carbon centers, bond equalization, and biradicaloid formation of the reactants. The transition state is aromatically stabilized and moved by five path units into the entrance channel in line with the Hammond-Leffler postulate. The pseudorotation of the boat form into the halfchair of cyclohexene is analyzed. Predictions are made for the Diels-Alder reaction based on a 11-phase mechanism obtained by t...Continue Reading

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Citations

Dec 15, 2017·Angewandte Chemie·Joshua H BarabanMichael C McCarthy
May 31, 2017·Chemphyschem : a European Journal of Chemical Physics and Physical Chemistry·Debdutta ChakrabortyPratim Kumar Chattaraj
Jun 27, 2019·Physical Chemistry Chemical Physics : PCCP·Sadisha Nanayakkara, Elfi Kraka
Apr 26, 2018·The Journal of Physical Chemistry. a·Dale A Braden, Chérif F Matta
Dec 10, 2019·The Journal of Physical Chemistry. a·Piotr OrdonLudwik Komorowski
Oct 12, 2021·Journal of Molecular Modeling·Marek FreindorfElfi Kraka

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