Biomass-derived polyols valorization towards glycolic acid production with high atom-economy

Taking advantage of the inherent structure in biomass for attractive chemical synthesis with high atom economy is vital for a sustainable future but remains a great challenge. Herein, we discovered a new route for glycolic acid (GcA) synthesis using various biomass-derived polyols as feedstock with an exceptionally high atom utilization (∼93 %). Up to ~90 C-mol% yield of GcA could be achieved, representing the highest value among the state-of-the-art biomass valorization strategies. Strongly certified by in situ experimental tests and multi-scale theoretical calculations, it was identified that dynamical accommodation of the flexible unsaturated dangling-like Cucus-O bond in Cu2O(111) to polyols drove electron transfer from polyols to Cucus, enabling the precise activation of C1-H and C2-C3 bonds. These contributions accomplished the complex cascade reactions in polyol transformation throughout chain-sugar as intermediate with notable conformation superiority, thus generating GcA selectively. [Display omitted] •Up to ~90 C-mol% yield of GcA was achieved from C4-polyol.•The reaction mechanism was revealed by situ HNMR and FTIR analyses.•Chain-sugar was the crucial intermediate with notable conformational superiority.•The accommodation between Cu/AC and polyols manipulated the catalytic activity.•C1-H and C2-C3 precise activation were realized by directional electron transfer.