An efficient approach to biomass-based tertiary amines by direct and consecutive reductive amination of furfural

• Published in: Journal of catalysis Vol. 410; pp. 164 - 179
• Main Authors: Lin, Chuncheng, Zhou, Jiamin, Zheng, Zhangfan, Chen, Jinzhu
• Format: Journal Article
• Language: English
• Published: Elsevier Inc 01.06.2022
• Subjects: Biomass; Furfural; Reductive amination; Rhodium phosphide; Tertiary amine; Reductive amination; Rhodium phosphide; Tertiary amine; Furfural; Biomass
• ISSN: 0021-9517; 1090-2694
• DOI: 10.1016/j.jcat.2022.04.016

Direct and consecutive reductive amination of furfural was developed with Rh2P catalyst for efficient synthesis of biomass-based tertiary amine. [Display omitted] •Biomass-based tertiary amines are developed for extension of amine chemistry.•Direct and consecutive reductive amination of furfural leads to tertiary amines.•Rh2P selectively and efficiently promotes the reactions with wide substrate scope.•Mechanism is supported by both experimental and theoretical investigations.•Excellent stability and recyclability of catalyst during consecutive recycling. Tertiary amines, currently obtained from fossil resources by a multi-step synthetic method, are important compounds in both chemical industry and organic transformations. Herein, we demonstrated highly efficient and convenient strategy to various biomass-based tertiary amines in excellent yields (85–95%) by a direct and consecutive reductive amination of furfural with various amines in one-pot using rhodium phosphide (Rh2P) catalyst. Typically, biomass-based tris(2-furanylmethyl)amine in 92% yield was directly obtained from furfural and HCOONH4 in one-step. Time-dependent reaction profiles suggested a consecutive amination/hydrogenation pathway with furfurylamine-derived Schiff base and secondary amine as successively detected intermediates. The superiority of Rh2P was ascribed to its excellent low-temperature hydrogenation activity, which is structurally attributed to an efficient electron-transfer from P atoms (on the P-terminated Rh2P) to their bonded and dissociated H atoms. This research thus highlights a powerful, elegant, and attractive approach to biomass-based tertiary amines for a sustainable extension of amine chemistry.