Catalytic Stereoselective Conversion of Biomass-Derived 4′-Methoxypropiophenone to <i>Trans</i>-Anethole with a Bifunctional and Recyclable Hf-Based Polymeric Nanocatalyst

Anethole (AN) is widely used as an odor cleaner in daily necessities, and can also be applied in the fields of food additives, drug synthesis, natural preservatives, and polymeric materials’ preparation. Considering environmental and economic benefits, the use of biomass raw materials with non-precious metal catalysts to prepare high-value fine chemicals is a very promising route. Here, we developed an acid-base bifunctional polymeric material (PhP-Hf (1:1.5)) composed of hafnium and phenylphosphonate in a molar ratio of 1:1.5 for catalytic conversion of biomass-derived 4′-methoxypropiophenone (4-MOPP) to AN via cascade Meerwein–Pondorf–Verley (MPV) reduction and dehydration reactions in a single pot. Compared with the traditional catalytic systems that use high-pressure hydrogen as a hydrogen donor, alcohol can be used as a safer and more convenient hydrogen source and solvent. Among the tested alcohols, 2-pentanol was found to be the best candidate in terms of pronounced selectivity. A high AN yield of 98.1% at 99.8% 4-MOPP conversion (TOF: 8.5 h−1) could be achieved over PhP-Hf (1:1.5) at 220 °C for 2 h. Further exploration of the reaction mechanism revealed that the acid and base sites of PhP-Hf (1:1.5) catalyst synergistically promote the MPV reduction step, while the Brønsted acid species significantly contribute to the subsequent dehydration step. In addition, the PhP-Hf polymeric nanocatalyst can be recycled at least five times, showing great potential in the catalytic conversion of biomass