Theoretical insight into the pyrolytic deformylation of levoglucosenone and isolevoglucosenone

•A computational study explains the pyrolytic deformylation of anhydrosugars.•Isolevoglucosenone deformylates more easily than levoglucosenone.•Isolevoglucosenone is slightly more reactive than levolgucosenone toward 3-oxidipyrylium.•Conceptual DFT and distortion/interaction analysis provide explanation for these findings.

A computational study was conducted to gain insight into the pyrolytic deformylations of levoglucosenone and isolevoglucosenone. Present B3LYP/6-31G∗ and CBS-QB3 calculations provide valuable evidence to rule out the formation of isolevoglucosenone during the pyrolytic degradation of cellulosic materials. This, along with the supplementary data herein presented and with other recent reports, suggest that levoglucosenone should not be formed directly from levoglucosan (as proposed in numerous reports), but rather from another intermediate, such as 1,4:3,6-dianhydro-α-d-glucopyranose.

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