The preparation of high value‐added chemicals from renewable resources is a crucial approach towards a sustainable economy. One prominent alternative to the production of petroleum‐based chemicals from fossil resources is through the sequential Diels‐Alder/aromatization reactions of biomass‐derived furan platforms. This Concept is focused on the recent boom in bio‐based furan DA strategies for aromatization of bio‐based platform chemicals, particularly that of furfurals, ranging from indirect use and activation strategies to recent examples of direct DA reaction of these electron‐withdrawing biomass‐derived furans.

The Diels–Alder (DA) reaction of biomass derived furans is an emerging technology for the preparation of new molecular entities and “drop-in” commodity chemicals. In this work, we address the challenge of the direct use of electron-poor furanic platforms as dienes through the use of an unexplored chitin derived furan, 3-acetamido-5-acetylfuran (3A5AF). The 3-acetamido group promoted a remarkable increase in the kinetics of the DA reaction, allowing for the preparation of 7-oxanorbornenes (7-ONBs) at 50 °C. Partial hydrolysis of enamide to hemi-acylaminals was possible upon fine-tuning of the reaction conditions, disabling retro-DA processes. Finally, the DA reaction of the reduced form of 3A5AF allowed quantitative formation of 7-ONBs under aqueous conditions after 10 minutes. Certainly, these are the first steps for expanding the toolbox of chitin derived 3A5AF as a diene.