Pioglitazone has been developed as an effective insulin-sensitizing agent for the treatment of type II diabetes mellitus. Selective hydrogenation of the benzylidenethiazolidinedione exocyclic alkene is a committed step in the industrial manufacturing of pioglitazone. However, the strong coordination between metallic sites of commercial hydrogenation catalysts and benzylidenethiazolidinedione might cause catalyst poisoning and lead to poor activity and selectivity. In this context, an effective and anti-poisoning catalyst with highly dispersed palladium nanoparticles supported on biomass-derived nitrogen-doped carbon with mesoporous structures has been established. A systematic investigation of the structure–activity relationship was performed with a series of Pd/CN_x by regulating the ratio of precursors D-glucosamine hydrochloride (GAH) and melamine, and it demonstrated that large specific surface area, rich pore structure and strong Pd–N interaction were essential for the high catalytic performance. The optimal Pd/CN_1.2 catalyst exhibited nearly 100% conversion and 95.5% selectivity under optimized reaction conditions. Remarkably, compared with commercial Pd/C catalyst, Pd/CN_1.2 displayed almost twice the catalytic productivity and provided better poisoning resistance and leaching resistance. Moreover, its stability was also acceptable and good activity could be maintained after exposed in the air for 4 months.

Graphical Abstract

中文翻译：

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抗中毒氮掺杂碳负载钯催化剂选择性加氢苯亚甲基噻唑烷二酮环烯烃

吡格列酮已被开发为治疗 II 型糖尿病的有效胰岛素增敏剂。亚苄基噻唑烷二酮环烯烃的选择性氢化是吡格列酮工业制造中的关键步骤。然而，商业加氢催化剂的金属位点与亚苄基噻唑烷二酮之间的强配位可能导致催化剂中毒并导致活性和选择性较差。在此背景下，建立了一种有效的抗中毒催化剂，该催化剂具有高度分散的钯纳米颗粒，负载在具有介孔结构的生物质衍生的氮掺杂碳上。通过调节前驱体D-葡萄糖胺盐酸盐（GAH）和三聚氰胺的比例，对一系列Pd/CN _x的构效关系进行了系统研究，结果表明，具有大的比表面积、丰富的孔结构和强的Pd –N相互作用对于高催化性能至关重要。优化的Pd/CN _1.2催化剂在优化的反应条件下表现出接近100%的转化率和95.5%的选择性。值得注意的是，与商业 Pd/C 催化剂相比，Pd/CN _1.2显示出几乎两倍的催化生产率，并提供更好的抗中毒性和抗浸出性。而且其稳定性也尚可，暴露在空气中4个月后仍能保持良好的活性。

图形概要