Selective hydrogenolysis of bio-renewable tetrahydrofurfurylamine to piperidine on ReOx-modified Rh catalysts

Piperidine is an important cyclic amine with versatile applications. However, its commercial process is not green and depends mainly on the hydrogenation of fossil resource-based pyridine. Here, we report a novel one-pot approach to the sustainable synthesis of piperidine from bio-renewable tetrahydrofurfurylamine (THFAM) via its hydrogenolysis to 5-amino-1-pentanol (APO) and the subsequent intramolecular amination of APO. SiO2-supported Rh-ReOx catalysts exhibited high efficiency and stability in the THFAM reaction to piperidine, providing a high yield of 91.5% at 200 degrees C and 2.0 MPa H-2 in water. Such high efficiency of Rh-ReOx/SiO2 was found to be related to the synergistic effect between the Rh nanoparticles and ReOx species on the kinetically-relevant cleavage of the C-O bond neighboring the C-NH2 group in THFAM, involving the strong adsorption of the C-NH2 group on ReOx and the heterolytic dissociation of H-2 on Rh. This work provides an efficient strategy for the selective cleavage of the C-O bonds neighboring the C-NH2 groups, irrespective of their presence in amino ethers or amino alcohols, and the green production of piperidine and its derivatives from biomass resources.

Automated summary

In this study, a novel green synthesis of piperidine from bio-renewable tetrahydrofurfurylamine (THFAM) is reported. The process involves the hydrogenolysis of THFAM to 5-amino-1-pentanol (APO) and the subsequent intramolecular amination of APO. SiO2-supported Rh-ReOx catalysts showed high efficiency and stability in converting THFAM to piperidine with a yield of 91.5% under the conditions of 200 degrees C and 2.0 MPa H-2 in water. The study provides an efficient strategy for the green production of piperidine and its derivatives from biomass resources.