Chemicals from Biomass: Selective Synthesis of N-Substituted Furfuryl Amines by the One-Pot Direct Reductive Amination of Furanic Aldehydes

Abstract

N-substituted furfuryl amines are an important class of compounds due to their pharmaceutical activities that can be produced by reductive amination of furfuraldehydes derived from biomass. With supported Pd nanoparticles it is possible to obtain high activities and selectivities for the production of secondary amines. CO adsorption monitored by IR show the importance of the Pd crystal size and crystal face on catalyst activity and selectivity. When using Pd on carbon the amount of unsaturated Pd sites is very much enhanced with the corresponding increase in selectivity. The role of carbon deposition on metal terraces on catalytic selectivity is discussed. The optimized catalyst has been successfully applied in the reductive amination of 5-hydroxymethylfurfural with different amines and ammonia as well as in the one-pot reductive amination starting from nitrobenzene instead of aniline, giving the different N-substituted-5-(hydroxymethyl)-2-furfuryl amines with excellent activity and selectivity.

Chemoenzymatic Synthesis of 5‐Hydroxymethylfurfural (HMF)‐Derived Plasticizers by Coupling HMF Reduction with Enzymatic Esterification

“…5‐Hydroxymethylfurfural (HMF), obtained by dehydration of hexoses, constitutes one of the most important and versatile platform molecules, owing to its broad range of potential applications in the biofuels and chemical industries. Numerous transformations of HMF, such as, oxidation, reduction, etherification, alkylation, aldol condensation, acetalization, hydration, and reductive amination, have been reported in recent years . Among them, the reduction of the formyl group of HMF to afford the symmetrical diol 2,5‐bis(hydroxymethyl)furan (BHMF), has received much attention .…”

Transforming Methyl Levulinate into Biosurfactants and Biolubricants by Chemoselective Reductive Etherification with Fatty Alcohols

“…The different catalysts, 5 % Pd/Al 2 O 3, 5 % Pd/TiO 2 , 5 % Pd/CeO 2 and (0.2, 0.5, 1.5, 2.5, 5, and 10 %) Pd/C were prepared through a deposition–precipitation method by mixing the appropriate amount of support powder with the appropriate amount of solution of palladium(II) acetylacetonate in toluene (10 mL) . After overnight stirring at room temperature, the solvent was evaporated, and the catalyst was dried at 100 °C in an oven, followed by reduction under H 2 stream (50 mL min −1 ) at 250 °C for 3 h . The physicochemical characteristics of the catalysts are presented in Tables S2 and S3 in the Supporting Information.…”

Cu‐Al mixed oxide derived from layered double hydroxide as an efficient catalyst for continuous‐flow reductive amination of aromatic aldehydes

“…Several methodologies have been developed to obtain secondary amines via N-alkylation of primary amines with alkyl halides 6 or alcohols, [6][7][8][9] Buchwald-Hartwig reaction, 10,11 and reductive amination of carbonyl compounds. [12][13][14][15][16][17][18][19][20][21][22][23][24][25][26] Among all these transformations, reductive amination over heterogeneous metal catalysts is a promising method due to the use of inexpensive and environmentally benign molecular hydrogen as a reducing agent. [15][16][17][18][19][20][21][22][23][24][25][26] This process involves reversible condensation of primary amine with aldehyde or ketone to form imine and the hydrogenation of imine into the secondary amine.…”