Advances in the Catalytic Reductive Amination of Furfural to Furfural Amine: The Momentous Role of Active Metal Sites

Abstract

One-pot synthesis of sustainable primary amines by catalytic reductive amination of bio-based carbonyl compounds with NH 3 and H 2 is emerging as a promising and robust approach. The primary amines, especially furfuryl amine (FUA) derived from furfural (FUR), with a wide range of applications from pharmaceuticals to agrochemicals, have attracted much attention due to their versatility. This Review is majorly comprised of two segments on the reductive amination of FUR to FUA, one with precious (Ru, Pd, Rh) and the other with nonprecious (Co, Ni) metals on different supports and in various solvent systems in the presence of NH 3 and H 2 . The active metal sites generated on multiple supports are accentuated with experimental evidence based on CO-diffuse reflectance infrared Fourier-transform spectroscopy, H 2 temperature-programmed reduction, X-ray photoelectron spectroscopy, and calorimetry. Moreover, this Review comprehensively describes the role of acidic and basic support for the metal on the yield of FUA. Overall, this Review provides an insight into how to design and develop an efficiently robust catalyst for the selective reductive amination of a broad spectrum of carbonyl compounds to corresponding amines.

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

“…Notably, such high selectivity and yield of piperidine (91.2%) were still obtained even when bio-furfural-derived furfurylamine was used directly as a reactant (Table 1, entry 3), due to the facile hydrogenation of furfurylamine to THFAM under the reductive conditions in this work. [43][44][45][46][47][48] Furthermore, the active carbon (C)-, ZrO 2 -and Nb 2 O 5 -supported Rh-ReO x (2 wt% Rh, 2.2 wt% Re) catalysts were examined with similar Rh particle sizes of 2.8-3.1 nm (TEM micrographs shown in Fig. S1 †).…”

“…Notably, such high selectivity and yield of piperidine (91.2%) were still obtained even when bio-furfural-derived furfurylamine was used directly as a reactant (Table 1, entry 3), due to the facile hydrogenation of furfurylamine to THFAM under the reductive conditions in this work. 43–48…”

Laccases from Pleurotus ostreatus Applied to the Oxidation of Furfuryl Alcohol for the Synthesis of Key Compounds for Polymer Industry

“…In order to show the applicability of our laccase‐TEMPO systems with POXA1b and POXC, the production of furfuryl amine ( 1 d ) from furfuryl alcohol was investigated through a one‐pot oxidation‐transamination sequence. This amine is a key monomer for polymers manufacturing; however, the traditional synthetic chemical methods require harsh operative steps, which often generate imines as intermediates, that can later form other by‐products, affecting therefore the final purity and yield of the desired compound [35] …”

“…This amine is a key monomer for polymers manufacturing; however, the traditional synthetic chemical methods require harsh operative steps, which often generate imines as intermediates, that can later form other by-products, affecting therefore the final purity and yield of the desired compound. [35] The sequential strategy was set-up using 50 mg of 1 a selecting amine transaminase from Chromobacterium violaceum (Cv-TA) [36] after optimization of the transamination reaction conditions. The transaminase reaction was run with a molar…”

Accelerated H2 activation over Pt/M-ZrO2 for the reductive amination of levulinic acid esters under benign conditions

“…In continuation of the above studies, altering the physicochemical properties of metal oxides (acidity, basicity, oxygen vacancies, and Lewis acid-base pair) has been investigated and found to strongly influence product distribution. [23][24][25][26][27][28][29][30][31][32][33][34] In line with this, Touchy et al 35 developed Mo-promoted Pt-MoO X /TiO 2 for the reductive amination of LA to OMP at 100 °C, 3 bar H 2 , obtaining a near quantitative yield (99%). Vidal et al 36 prepared Pt/TiO 2 via the deposition-precipitation method for the reductive amination of ethyl levulinate, affording a high selectivity towards the target product at 120 °C under solvent-free conditions.…”