Substituted anilides from chitin-based 3-acetamido-furfural

• Published in: Organic & biomolecular chemistry Vol. 21; no. 41; pp. 8372 - 8378
• Main Authors: van der Loo, Cornelis H. M, Kaniraj, J. P, Wang, Ting, Broekman, J. O. P, Borst, Mark L. G, Pouwer, Kees, Heeres, André, Deuss, Peter J, Minnaard, Adriaan J
• Format: Journal Article
• Language: English
• Published: CAMBRIDGE Royal Soc Chemistry 25.10.2023; Royal Society of Chemistry
• Subjects: Acetic anhydride; Aldehydes; Aromatic compounds; Cascade chemical reactions; Chemistry; Chemistry, Organic; Chitin; Furans; Furfural; Hydrazones; Pesticides; Phthalimide; Phthalimides; Physical Sciences; Pyrrolidine; Science & Technology; Substitutes; Synthesis; CYCLOADDITION; AROMATICS; D-GLUCOSAMINE; CONVERSION; BIOMASS
• ISSN: 1477-0520; 1477-0539
• DOI: 10.1039/d3ob01461d

The synthesis of aromatic compounds from biomass-derived furans is a key strategy in the pursuit of a sustainable economy. Within this field, a Diels-Alder/aromatization cascade reaction with chitin-based furans is emerging as a powerful tool for the synthesis of nitrogen-containing aromatics. In this study we present the conversion of chitin-based 3-acetamido-furfural ( 3A5F ) into an array of di- and tri-substituted anilides in good to high yields (62-90%) via a hydrazone mediated Diels-Alder/aromatization sequence. The addition of acetic anhydride expands the dienophile scope and improves yields. Moreover, replacing the typically used dimethyl hydrazone with its pyrrolidine analogue, shortens reaction times and further increases yields. The hydrazone auxiliary is readily converted into either an aldehyde or a nitrile group, thereby providing a plethora of functionalized anilides. The developed procedure was also applied to 3-acetamido-5-acetylfuran ( 3A5AF ) to successfully prepare a phthalimide. A Diels-Alder/aromatization cascade reaction with chitin-based furans is a powerful tool for the synthesis of nitrogen-containing aromatics.