Dynamic trapping as a selective route to renewable phthalide from biomass-derived furfuryl alcohol
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A novel route for the production of the versatile chemical building block phthalide from biorenewable furfuryl alcohol and acrylate esters is presented. Two challenges that limit sustainable aromatics production via Diels–Alder (DA) aromatisation—an unfavourable equilibrium position and undesired regioselectivity when using asymmetric addends—were addressed using a dynamic kinetic trapping strategy. Activated acrylates were used to speed up the forward and reverse DA reactions, allowing for one of the four DA adducts to undergo a selective intramolecular lactonisation reaction in the presence of a weak base. The adduct is removed from the equilibrium pool, pulling the system completely to the product with a fixed, desired regiochemistry. A single 1,2-regioisomeric lactone product was formed in up to 86 % yield and the acrylate activating agent liberated for reuse. The lactone was aromatised to give phthalide in almost quantitative yield in the presence of Ac2O and a catalytic amount of strong acid, or in 79 % using only catalytic acid.
Lancefield , C S , Fölker , B , Cioc , R C , Stanciakova , K , Bulo , R E , Lutz , M , Crockatt , M & Bruijnincx , P C A 2020 , ' Dynamic trapping as a selective route to renewable phthalide from biomass-derived furfuryl alcohol ' , Angewandte Chemie - International Edition , vol. Early View . https://doi.org/10.1002/anie.202009001
Angewandte Chemie - International Edition
Copyright © 2020 The Authors. Published by Wiley-VCH GmbH. This is an open access article under the terms of the Creative Commons Attribution‐NonCommercial‐NoDerivs License, which permits use and distribution in any medium, provided the original work is properly cited, the use is non‐commercial and no modifications or adaptations are made.
DescriptionR.B. acknowledges the Netherlands Organization for Scientific Research (NWO) (Vidi 723.012.104). C.S.L. thanks the Leverhulme Trust Early Career Fellowship (ECF‐2018‐480). We also acknowledge the NWO for funding the X‐ray diffractometer used in this study. K.S. acknowledges financial support from The Netherlands Centre for Multiscale Catalytic Energy Conversion (MCEC).
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