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.

中文翻译：

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用双功能和可回收的 Hf 基聚合物纳米催化剂催化立体选择性转化生物质衍生的 4'-甲氧基苯丙酮为反式茴香脑

茴香脑（AN）在日用品中广泛用作除味剂，还可用于食品添加剂、药物合成、天然防腐剂、高分子材料制备等领域。考虑到环境和经济效益，利用生物质原料配合非贵金属催化剂制备高价值精细化学品是一条非常有前景的路线。在这里，我们开发了一种酸碱双功能聚合物材料 (PhP-Hf (1:1.5))，由摩尔比为 1:1.5 的铪和苯基膦酸酯组成，用于催化转化生物质衍生的 4'-甲氧基苯丙酮 (4-MOPP)通过级联 Meerwein-Pondorf-Verley (MPV) 还原和脱水反应在一个锅中转化为 AN。与使用高压氢气作为供氢体的传统催化系统相比，酒精可以作为更安全、更方便的氢源和溶剂。在测试的醇中，发现 2-戊醇是具有显着选择性的最佳候选者。AN 产率高达 98.1%，4-MOPP 转化率为 99.8%（TOF：8.5 小时）^-1 ) 可以通过 PhP-Hf (1:1.5) 在 220 °C 下达到 2 小时。对反应机理的进一步探索表明，PhP-Hf (1:1.5) 催化剂的酸位和碱位协同促进 MPV 还原步骤，而布朗斯台德酸物质对随后的脱水步骤有显着贡献。此外，PhP-Hf聚合物纳米催化剂至少可以回收5次，在生物质催化转化方面显示出巨大潜力。