Searching for sustainable polymers requires access to biomass-based monomers. In that sense, glucose-derived cis,cis-muconic acid stands as a high-potential intermediate. However, to unlock its potential, an isomerization to the value-added trans,trans-isomer, trans,trans-muconic acid, is required. Here we develop atomically dispersed low-loaded Ru on beta zeolite catalysts that produce trans,trans-muconate in ethanol with total conversion (to equilibrium) and a selectivity of >95%. We reach very high turnovers per Ru and productivity rates of 427 mM h⁻¹ (~85 g l⁻¹ h⁻¹), surpassing the bio-based cis,cis-muconic acid production rates by an order of magnitude. By coupling isomerization to Diels–Alder cycloaddition, terephthalate intermediates are produced in around 90% yields, circumventing the isomer equilibrium. Isomerization is promoted by Ru hydride species where the hydrides are generated from the alcohol solvent, as evidenced by Fourier transform infrared spectroscopy. Beyond isomerization, the Ru–zeolite and its hydride-forming capacity could be of use as a heterogeneous catalyst for other hydride chemistries, demonstrated by a successful hydride transfer hydrogenation.

寻找可持续聚合物需要获得基于生物质的单体。从这个意义上说，葡萄糖衍生的顺式，顺式粘康酸是一种高潜力的中间体。然而，为了释放其潜力，需要异构化为增值的反式、反式异构体、反式、反式粘康酸。在这里，我们开发了原子分散的低负载 Ru β 沸石催化剂，该催化剂可在乙醇中产生反式、反式粘康酸酯，总转化率（达到平衡）和选择性为 >95%。我们达到了非常高的每 Ru 周转率和 427 mM h ⁻¹ (~85 gl ⁻¹ h ⁻¹ ) 的生产率，超过生物基顺式、顺式粘康酸生产率一个数量级。通过将异构化与狄尔斯-阿尔德环加成耦合，对苯二甲酸酯中间体的产率约为 90%，从而绕过了异构体平衡。傅里叶变换红外光谱证明，异构化是由 Ru 氢化物物质促进的，其中氢化物是从醇溶剂中产生的。除了异构化之外，Ru-沸石及其氢化物形成能力还可以用作其他氢化物化学的非均相催化剂，这一点已通过成功的氢化物转移氢化得到证明。