Beijing National Laboratory for Molecular Science, CAS Key Laboratory of Colloid and Interface and Thermodynamics, CAS Research/Education Center for Excellence in Molecular Sciences, Institute of Chemistry , Chinese Academy of Sciences , Beijing 100190 , China.
School of Chemistry and Chemical Engineering , University of Chinese Academy of Sciences , Beijing 100049 , China.
J Am Chem Soc. 2019 Mar 6;141(9):4002-4009. doi: 10.1021/jacs.8b13024. Epub 2019 Feb 20.
Construction of N-substituted pyrrolidones from biomass-derived levulinic acid (LA) via reductive amination is a highly attractive route for biomass valorization. However, realizing this transformation using H as the hydrogen source under mild conditions is still very challenging. Herein, we designed porous TiO nanosheets-supported Pt nanoparticles (Pt/P-TiO) as the heterogeneous catalyst. The prepared Pt/P-TiO was highly efficient for reductive amination of LA to produce various N-substituted pyrrolidones (34 examples) at ambient temperature and H pressure. Meanwhile, Pt/P-TiO showed good applicability for reductive amination of levulinic esters, 4-acetylbutyric acid, 2-acetylbenzoic acid, and 2-carboxybenzaldehyde. Systematic studies indicated that the strong acidity of P-TiO and the lower electron density of the Pt sites as well as the porous structure resulted in the excellent activity of Pt/P-TiO.
从生物质衍生的乙酰丙酸（LA）通过还原胺化来构建 N-取代的吡咯烷酮是生物质增值的一种极具吸引力的途径。然而，在温和条件下使用 H 作为氢源来实现这种转化仍然极具挑战性。在此，我们设计了多孔 TiO 纳米片负载的 Pt 纳米粒子（Pt/P-TiO）作为多相催化剂。所制备的 Pt/P-TiO 在环境温度和 H 压力下对 LA 的还原胺化具有很高的效率，可生成各种 N-取代的吡咯烷酮（34 个实例）。同时，Pt/P-TiO 对乙酰丙酸酯、4-乙酰丁酸、2-乙酰苯甲酸和 2-羧基苯甲醛的还原胺化也具有很好的适用性。系统研究表明，P-TiO 的强酸性、Pt 位的较低电子密度以及多孔结构导致了 Pt/P-TiO 的优异活性。
