During autocatalyzed steam explosion of lignocellulose, polysaccharides in the cell wall are hydrolyzed and dehydrated to form various furaldehydes. In addition to furfural, 5-methylfurfural and 2-acetylfuran were identified in condensates from autocatalyzed steam explosion of Scandinavian softwood (Norway spruce, Picea abies). The presence of 5-methylfurfural can be explained by an acid-catalyzed dehydration of 6-deoxyaldohexoses, which are known to be present in lignocellulosic biomass. However, the presence of 2-acetylfuran cannot be explained by previously published reaction mechanisms since the required substrate (a 1-deoxyhexose or a 1-deoxyhexosan) is not known to be present in lignocellulosic biomass. In model experiments, it was shown that 2-acetylfuran is formed from rhamnose and fucose upon heating in the presence of the Lewis acid Cr3+. Possible reaction pathways for the formation of 2-acetylfuran from 6-deoxyaldohexoses are suggested. This reaction can potentially enable the targeted production of 2-acetylfuran from renewable biomass feedstocks. © 2022 The Authors