Dynamic Trapping as a Selective Route to Renewable Phthalide from Biomass-Derived Furfuryl Alcohol.

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 Ac2 O and a catalytic amount of strong acid, or in 79 % using only catalytic acid. © 2020 The Authors. Published by Wiley-VCH GmbH.

Citation

Christopher S Lancefield, Bart Fölker, Razvan C Cioc, Katarina Stanciakova, Rosa E Bulo, Martin Lutz, Marc Crockatt, Pieter C A Bruijnincx. Dynamic Trapping as a Selective Route to Renewable Phthalide from Biomass-Derived Furfuryl Alcohol. Angewandte Chemie (International ed. in English). 2020 Dec 21;59(52):23480-23484

Mesh Tags

Substances

PMID: 32885556

search → result