5-Methylfurfural (MF) is a critical commodity chemical used as food additive and synthetic intermediate. Opening a sustainable route towards highly selective synthesis of MF from 5-hydroxymethylfurfural (HMF) is of great significance, but has demonstrated extremely challenging. Herein, we report an efficient process for the selective production of MF from HMF over an anatase-supported gold catalyst (Au/a-TiO₂). During the hydrogenolysis of HMF, the desired CO bond is maintained and MF can be obtained in a high yield of 83.1 %, exhibiting excellent stability both in batch and flow operation. A combination of experimental and theoretical analyses attribute the superior performance of Au/a-TiO₂ to the synergistic effect of limited H access, low adsorption of reactants, and avoiding condensation, driven by the high concentration of oxygen vacancies in the support. This study highlights a novel approach of tailoring the coverage of active species for the selective transformation of renewable compounds into high-value-added chemicals.

5-甲基糠醛 (MF) 是一种重要的商品化学品，用作食品添加剂和合成中间体。开辟一条从 5-羟甲基糠醛 (HMF) 高选择性合成 MF 的可持续途径具有重要意义，但已证明极具挑战性。_{在此，我们报告了一种通过锐钛矿负载金催化剂 (Au/a-TiO 2} )从 HMF 选择性生产 MF 的有效工艺。在 HMF 的氢解过程中，所需的 C O 键得以保持，并且可以以 83.1% 的高产率获得 MF，在间歇和流动操作中都表现出优异的稳定性。实验和理论分析的结合归功于 Au/a-TiO _{2的优越性能}在载体中高浓度氧空位的驱动下，H 访问受限、反应物吸附低和避免缩合的协同效应。这项研究强调了一种新方法，该方法可以调整活性物种的覆盖范围，以将可再生化合物选择性地转化为高附加值化学品。