Abstract
AbstractAlthough different ways of converting 5‐(hydroxymethyl)furfural (1) to various substrates with high value have been sought, few transformations have obtained building blocks that can be very useful in the area of fine chemistry. Herein, we report the synthesis of protoanemonin (5‐methylenefuran‐2(5H)‐one) from D‐fructose via compound (1), a versatile γ‐alkylidenebutenolide, using an efficient self‐catalysed process with formic acid, with high reaction performance and selectivity (up to 94% yield and 98% conversion from (1), while 28% yield from D‐fructose). This efficient and simple operational process involved a two‐phase aqueous‐organic system between chlorinated solvents (CHxCly) and hydrogen peroxide as the initial oxidizing agent. The reaction presents a key cleavage in the 5‐hydroxymethyl moiety of (1), due to the Baeyer‐Villiger oxidation (BVO) process that generates formic acid in situ. Ultimately, DFF and HMF were successfully obtained in 80% and 98% yield, respectively, starting from D‐fructose and using Preyssler heteropolyacids as Brønsted acid catalysts under an atmosphere of oxygen in the absence of hydrogen peroxide.
Highlights
The transformation of renewable biomass resources into valuable chemicals has received great attention due to their abundance and is a promising sustainable alternative for the production of important intermediates at low cost
The oxidation of furfural to produce dicarboxylic acids has been extensively studied;[3] the yields depend on the type of substituent on the furan ring,[3a,b] reaction temperature, and the amount of oxidant agent employed.[3d]. It is importat to note that diverse transformations of HMF into DFF, anhydride maleic, and maleic acid are conducted with vanadium-based catalysts under molecular oxygen atmosphere.[4]
A notable aspect of these catalysts is the oxidative scission of the C−C bond between hydroxymethyl fragment and furan ring into HMF for the selective formation of the maleic anhydride and its derivatives, according to the previously reported electron transfer and oxygen transfer reaction mechanism (ET-OT).[4]
Summary
A sister journal of Chemistry – An Asian Journal and European Journal of Organic Chemistry. Romanelli,[b,c] Jaime Portilla,[d] Juan-Carlos Castillo,[a,d] and Diana Becerra*[a]
Sign-in/Register to view highlights & summary Sign-in/Register to access full text options 
Free) 
Talk to us
Join us for a 30 min session where you can share your feedback and ask us any queries you have
Schedule a call
