Modulating Reactivity and Selectivity of 2-Pyrone-Derived Bicyclic Lactones through Choice of Catalyst and Solvent

作者：Pfennig Toni; Chernburkar Ashwin; Johnson Robert L; Ryan Matthew J; Rossini Aaron J; Neurock Matthew; Shanks Brent H^*

来源：ACS Catalysis, 2018, 8(3): 2450-2463.

DOI：10.1021/acscatal.7b04311

• coumalic acid diversification
• renewable dihydrobenzenes
• renewable aromatics
• benzoic acid
• isophthalic acid
• decarboxylation
• Diels-Alder

2-Pyrones, such as coumalic acid, are promising biobased molecules that through Diels-Alder reactions can provide access to a wide range of biobased chemicals, including molecules with functionality that are not easily accessible via conventional petrochemical routes. A complete reaction network and kinetic parameters for three individual diversification routes that start from a single bicyclic lactone produced via the Diels-Alder cycloaddition of coumalic acid and ethylene were examined experimentally and probed through complementary first-principle density functional theory (DFT) calculations, in situ nuclear magnetic resonance (NMR) spectroscopy, and thin film solid-state NMR spectroscopy. These experiments provide insights into the routes for several molecular structures from bicyclic lactones by leveraging Lewis or Bronsted acid catalysts to selectively alter the reaction pathway. The bicyclic lactone bridge can be decarboxylated to access dihydrobenzenes at a substantially reduced activation barrier using gamma-Al2O3 as the catalyst or selectively ring-opened via Bronsted acids to yield 1,3-diacid six membered rings. DFT computations and microkinetic modeling in combination with experimental results provide molecular insights into the catalytically active sites on gamma-Al2O3 and provide a general mechanism for the catalyzed bicyclic lactone decarboxylation in polar aprotic solvents, which involves CO2 extrusion as the kinetically relevant step. Solid-state NMR spectroscopy provides direct evidence of strong binding of the bicyclic lactone to the gamma-Al2O3 surface, fully consistent with DFT simulation results and experimental reaction kinetics. In addition, the role of the solvent was examined and found to be an additional means to improve reaction rates and selectively produce alternative structures from the bicyclic intermediate. The rate of the decarboxylation reaction was increased dramatically by using water as the solvent whereas methanol acted as a nucleophile and selectively induced ring-opening, showing that both pathways are operative in the absence of catalyst. Taken together, the results demonstrate an approach for selective diversification of the coumalate platform to a range of molecules.

• 出版日期2018-3