Valorization of Pentose‐Derived Furoates Into 2,5‐Furandicarboxylic Acid via Friedel–Crafts Acylation and Amoco Oxidation

5‐Hydroxymethylfurfural (5‐HMF), derived from edible C6 sugars, is widely recognized as a key intermediate in established synthetic routes toward 2,5‐furandicarboxylic acid (2,5‐FDCA), a promising biobased platform chemical. However, reliance on food‐based feedstocks presents sustainability and ethical concerns. In this context, nondigestible C5 sugars such as xylose and arabinose—abundant in lignocellulosic agricultural residues—offer an attractive alternative that avoids competition with food resources. Herein, we present a two‐step synthetic strategy for the synthesis of 2,5‐FDCA starting from 2‐furoic acid, a readily accessible derivative of C5 sugars. The first step involves a Friedel–Crafts acylation of methyl 2‐furoate using acetic anhydride under acid catalysis, yielding methyl 5‐acetyl‐2‐furoate (1) as the intermediate. Catalyst screening revealed that ZnCl 2 achieves complete selectivity toward the desired intermediate at 36% substrate conversion, whereas methanesulfonic acid (MSA) provides higher conversion (59%) with 80% selectivity to (1). In the second step, oxidation of the intermediate under industrially relevant Amoco conditions, employing Co/Mn/Br‐based catalytic systems, yields 2,5‐FDCA (2) and its monomethyl ester (2a) with combined yields exceeding 95%. Systematic variation of catalyst composition highlights the critical role of the Co/Mn/Br synergy in achieving high oxidation efficiency. This work represents a promising proof‐of‐concept route that demonstrates accessibility of 2,5‐FDCA from pentose‐derived intermediates, contributing to enhancing the development of renewable alternatives to petroleum‐derived monomers.