Title
Rolf Huisgen’s Classic Studies of Cyclic Triene Diels-Alder Reactions Elaborated by Modern Computational Analysis.
DOI
10.1002/anie.202003279
Abstract
Rolf Huisgen explored the Diels–Alder reactions of 1,3,5-cycloheptatriene (CHT) and cyclooctatetraene (COT) with the dienophiles maleic anhydride and 4-phenyl-1,2,4-triazoline-3,5-dione (PTAD) to determine the kinetics and mechanisms of various electrocyclizations and Diels–Alder reactions. These reactions have been examined with density functional theory. Modern computational chemistry has provided information not previously available by experiment. Transition states for all the reactions have been identified, and their Gibbs energies are used to explain the experimental reactivities. Zwitterionic intermediates were not found in the [4+2] cycloadditions of both CHT or COT with PTAD and are thus not involved in these reactions. [2+2+2] cycloadditions, as an alternative path to the Diels–Alder products, are highly disfavored. Rapid double nitrogen inversion was found for the cycloaddition products with PTAD.
Document Type
Article
Publication Date
5-25-2020
Publisher Statement
Copyright © 2020, John Wiley & Sons, Ltd.
Recommended Citation
Chen, Pan-Pan, Jeffrey I. Seeman, and Kendall N. Houk. “Rolf Huisgen’s Classic Studies of Cyclic Triene Diels-Alder Reactions Elaborated by Modern Computational Analysis.” Angewandte Chemie-International Edition Forthcoming (May 5, 2020). https://doi.org/10.1002/anie.202003279.