The dehydro-Diels–Alder reaction is a powerful synthetic method for preparing highly unsaturated six-membered rings when the initial Diels–Alder adduct involves a cumulated cyclohexadienyl intermediate. However, when the reaction involves the de-aromatization of a heteroarene to produce a 1,4-cyclohexadienyl intermediate, harsh conditions and the formation of multiple products compromise its synthetic utility. We are using an iterative process involving experiment and computation to identify factors that influence reactivity and selectivity to expand the reaction scope. DFT transition state calculations and experimentally derived Gibbs free energies of activation are correlated for reactivity determinations. Identification of factors influencing product selectivity are accomplished by experimentally measuring product ratios under a variety of reaction conditions for precursors that differ electronically and sterically. The results from these experiments are guiding the computational studies required for selectivity determination. We will present our findings and mechanistic insight from these reactivity and selectivity studies.

Determination of reactivity and selectivity for the dearomative dehydro-Diels-Alder reaction of heteroarenes

Macromolecular Chemistry: The Second Century

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ACS Spring 2020 National Meeting & Expo

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