Photocatalytic Achmatowicz\nRearrangement on Triphenylbenzene–Dimethoxyterephthaldehyde–Covalent\nOrganic Framework-Mo for Converting Biomass-Derived Furfuryl Alcohol\nto Hydropyranone

The conversion of biomass-based feedstocks into high-value\nplatform\ncompounds remains a fundamental but challenging topic. Studies on\nsuch transformations are sparse due to the complex nature of biomass\nand limited upgrading strategies. Photocatalytic aerobic oxidation\nis a promising pathway for making pharmaceutical precursors from biomass-derived\nchemicals. In this study, we demonstrate the transformation of furfuryl\nalcohol into dihydropyranone acetyl by using a molybdenum-incorporated\ntriphenylbenzene–dimethoxyterephthaldehyde–covalent\norganic framework <i>via</i> a singlet oxygen (<sup>1</sup>O<sub>2</sub>)-mediated photocatalytic Achmatowicz reaction. The\nCOF-Mo photocatalyst exhibits exceptional selectivity up to 98% in\nproducing hydroxy-2H-pyran-3(6H)-one, a complex synthone crucial for\nsynthesizing anti-AIDS drugs. Mo incorporation enhances the generation\nrate by 3.9 times, primarily due to the synergistic effect between\nMo active sites and the COF backbone. More importantly, Mo clusters\ncreate a superfast charge tunnel for photogenerated electron transfer\nfrom COF to adsorbed O<sub>2</sub>. The metallic state and hexavalent\nof Mo facilitate the generation of superoxide anions and <sup>1</sup>O<sub>2</sub>, respectively, facilitating photocatalytic reactions.