N-formyl-stabilizing quasi-catalytic species afford rapid and selective solvent-free amination of biomass-derived feedstocks

Abstract

Nitrogen-containing compounds, especially primary amines, are vital building blocks in nature and industry. Herein, a protocol is developed that shows in situ formed N-formyl quasi-catalytic species afford highly selective synthesis of formamides or amines with controllable levels from a variety of aldehyde- and ketone-derived platform chemical substrates under solvent-free conditions. Up to 99% yields of mono-substituted formamides are obtained in 3 min. The C-N bond formation and N-formyl species are prevalent in the cascade reaction sequence. Kinetic and isotope labeling experiments explicitly demonstrate that the C-N bond is activated for subsequent hydrogenation, in which formic acid acts as acid catalyst, hydrogen donor and as N-formyl species source that stabilize amine intermediates elucidated with density functional theory. The protocol provides access to imides from aldehydes, ketones, carboxylic acids, and mixed-substrates, requires no special catalysts, solvents or techniques and provides new avenues for amination chemistry.

Visible-light-driven amino acids production from biomass-based feedstocks over ultrathin CdS nanosheets

“…Several methods such as Strecker synthesis 6 have long been established, however, highly toxic cyanides and non-renewable aldehydes are used as substrates preventing their large-scale application 7,8 . The chemical routes to transform renewable organic carbon feedstocks and cheap, abundant NH 3 into amino acids 9,10 , and other relevant nitrogen-containing chemicals [11][12][13][14][15][16] in an energy-saving manner are highly desirable. For example, an exciting progress has recently been reported on the sustainable synthesis of glycine and alanine by catalytic fixation of N 2 and CO 2 17 .…”

Cycloamination strategies for renewable N-heterocycles

“…[23][24][25][26] Nitrogenous compounds hold a privileged position in the preparation of drugs, agrochemicals, polymers, and other functional materials. 27,28 In particular, nitrogen species are presented in more than 80% of the top 200 pharmaceuticals, 29,30 and two thirds of these N-containing medicines contain N-heterocyclic skeletons. 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.…”

Functionalized Metal-Organic Framework Catalysts for Sustainable Biomass Valorization

“…Among them, high specific surface areas, tunable acidity, porous nanostructures, and bifunctionality such us Brønsted-Lewis acidic, acidic-basic, and metal nanoparticle-acidic or basic play a pivotal role in efficient heterogeneous catalytic procedures. Generally, the biomass conversion processes are composed of a series of tandem reactions [20][21][22][23][24].…”