Low‐Temperature Reductive Aminolysis of Carbohydrates to Diamines and Aminoalcohols by Heterogeneous Catalysis

Abstract

Short amines, such as ethanolamines and ethylenediamines, are important compounds in today's bulk and fine chemicals industry. Unfortunately, current industrial manufacture of these chemicals relies on fossil resources and requires rigorous safety measures when handling explosive or toxic intermediates. Inspired by the elegant working mechanism of aldolase enzymes, a novel heterogeneously catalyzed process-reductive aminolysis-was developed for the efficient production of short amines from carbohydrates at low temperature. High-value bio-based amines containing a bio-derived C2 carbon backbone were synthesized in one step with yields up to 87 C%, in the absence of a solvent and at a temperature below 405 K. A wide variety of available primary and secondary alkyl- and alkanolamines can be reacted with the carbohydrate to form the corresponding C2-diamine. The presented reductive aminolysis is therefore a promising strategy for sustainable synthesis of short, acyclic, bio-based amines.

En route to CO2-containing renewable materials: catalytic synthesis of polycarbonates and non-isocyanate polyhydroxyurethanes derived from cyclic carbonates

“…154 The formation of biobased diamines is also possible from lignin derivatives when ammonia is added into the reaction mixture as a reagent. 155,156 Currently, ammonia is generated from the Haber-Bosch (HB) process, but efforts to produce more sustainable ammonia are underway. 157 The synthesis of ammonia (Haber-Bosch) is energy-intensive and, therefore, the biopolymers chitin and chitosan are being investigated as alternative sources of nitrogen containing compounds.…”

Effective synthesis of 5-amino-1-pentanol by reductive amination of biomass-derived 2-hydroxytetrahydropyran over supported Ni catalysts

“…These processes generally suffer from high cost due to the lack of organic feedstocks with special functional group(s) or the generation of large amounts of waste. Therefore, much attention has been paid to the development of new catalytic processes for the efficient and sustainable production of primary amines [2,[4][5][6][7][8][9].…”

“…It is known that carbonyl intermediates are usually generated during the preparation of alcohols (including diols) by transforming renewable lignocellulose and its derived platform molecules [9,[14][15][16]. Therefore, the coupling of the formation of renewable aldehydes or ketones and their reductive amination may shed light on the sustainable synthesis of amines with high efficiency [2,8,9,14]. For instance, Zhang and coworkers [9] recently reported the first example of the direct conversion of cellulose into highly useful ethanolamines by a two-step approach: cellulose conversion to glycolaldehyde, followed by reductive amination.…”

“…Ethanolamine with 10% yield was obtained from cellulose over a Ru/ZrO2 catalyst at a low temperature of 75 °C, and a high (93%) ethanolamine yield could be achieved using glycolaldehyde as a reactant. Sels et al [8] reported a new process for the efficient synthesis of short amines from carbohydrates by reductive aminolysis of the short carbonyl intermediates from the enzymatic retro-aldol C-C bond scission of the sugar molecule. Valuable bio-based amines with yields of up to 87% were attained in one step at a temperature below 132 °C.…”

Cycloamination strategies for renewable N-heterocycles

“…31 Given the above considerations, urgent attention is needed to develop green and efficient approaches to task-specific azaheterocycles from renewable biomass feedstocks via sustainable chemistry. The employed nitrogen sources can be derived from ammonia, amines/amides pre-prepared by C-N coupling reactions (e.g., reductive amination, aminolysis, and amidation), [32][33][34][35][36] or natural N-reservoirs (e.g., chitin, proteins) for producing amines and derivatives (e.g., glucosamine, N-acetyl-D-glucosamine, amino acids). [37][38][39][40][41] Beginning from the accessible bio-based functional molecules, N-heterocycles can be constructed by C-N and/or C-C bond formation typically via three dominant synthetic routes including intramolecular cyclization, cycloaddition (e.g., aza-Diels-Alder), and multicomponent condensation reactions (Fig.…”