2-pyrones such as Coumolic acid are versatile bio-privileged intermediates derived from biomass that can readily be reacted with different dienophiles to produce stable bicyclic lactone intermediates. These intermediates can subsequently be ring-opened to dihydrobenzene as well as a slate of other functionalized intermediates with selectivities of &gt; 90% at 100% conversion. These partially saturated intermediates can subsequently be dehydrogenated over metal centers to produce functionalize aromatic products with unique properties as antimicrobial agents, insecticides, and pharmaceuticals. First principle theoretical calculations were carried out together with in-situ 2D-NMR experiments and detailed kinetic studies to elucidate the mechanisms for Diels-Alder, retro-Diels Alder and dehydrogenation paths that control this chemistry. The use of Pd/Al2O3 resulted in high yields of benzoic acid. The nature of the acid sites, Brønsted vs. Lewis and the presence of different solvents provided unique opportunities to drive ring opening reactions, methanolysis to enable a diverse suite of products. Herein we discuss the results from density functional theoretical calculations on the role of acid and metal sites in carry out this chemistry and the influence of polar solvents such as water and methanol.

Controlling catalytic activity and selectivity of bioprivileged 2-pyrone platform intermediates to functionalized aromatics: The influence of acid sites and solvents

256th National Meeting (2018)

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