Theoretical Explanation for How SO3H‐Functionalized Ionic Liquids Promote the Conversion of Cellulose to Glucose

While the catalytic transformation of cellulose to glucose by functionalized ionic liquids (ILs) has been achieved successfully under mild conditions, insight into the fundamental molecular mechanism is still lacking. The present work presents the first attempt to address the fundamental reaction chemistry of the catalytic transformation. An enzyme‐like catalytic mechanism of ILs, in which glycosidic bond hydrolysis proceeds through a retaining mechanism and/or an inverting mechanism, is proposed. DFT calculations show that both mechanisms involve moderate barriers (<30 kcal mol^?1), which is consistent with the catalytic performance of the ILs under mild conditions (<100 °C). The “biomimetic” mechanism model proposed herein is expected to be viable for understanding the unique catalytic activity of ILs under mild conditions.