Unlocking the Potential of Bio‐Based Nitrogen‐Rich Furanic Platforms as Biomass Synthons

The demand for new biomass‐derived fine and commodity chemicals propels the discovery of new methodologies and synthons. Whereas furfural and 5‐hydroxymethylfurfural are cornerstones of sustainable chemistry, 3‐acetamido‐5‐acetyl furan (3A5AF), an N‐rich furan obtained from chitin biomass, remains unexplored, due to the poor reactivity of the acetyl group relative to previous furanic aldehydes. Here we developed a reactive 3‐acetamido‐5‐furfuryl aldehyde (3A5F) and demonstrated the utility of this synthon as a source of bio‐derived nitrogen‐rich heteroaromatics, carbocycles, and as a bioconjugation reagent. In this work we overcome current limitations of biomass furanic platforms, namely the lack of sustainable nitrogen in cellulose‐based furfurals and the lack of reactivity of chitin‐based ones. To this end, a tandem dehydration/oxidative cleavage of N‐acetylglucosamine delivers a new nitrogen‐rich furfural. We further demonstrate the utility of the new furan as a valuable monomer for synthetic chemistry and as a bioconjugation tool.