The electrochemical oxidation of amines to nitriles and imines represents a critical frontier in organic electrochemistry, offering a sustainable pathway to these valuable compounds. Nitriles and amines are pivotal in various industrial applications, including pharmaceuticals, agrochemicals, and materials science. This review encapsulates the recent advancements in the electrooxidation process, emphasizing mechanistic understanding, electrode material innovations, optimization of reaction conditions, and exploration of solvent and electrolyte systems. Additionally, the review addresses the operational parameters that significantly affect the electrooxidation process, such as current density, temperature, and electrode surface, offering insights into their optimization for enhanced performance. By providing a comprehensive view of the current state and prospects of amine electrooxidation to nitriles and imines, this review aims to inspire further development, innovation, and research in this promising area of green chemistry.
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http://dx.doi.org/10.1021/acsorginorgau.4c00025 | DOI Listing |
J Colloid Interface Sci
December 2024
College of Chemical and Biological Engineering, Zhejiang Provincial Key Laboratory of Advanced Chemical Engineering Manufacture Technology, Zhejiang University, 310027, Hangzhou, PR China; Zhejiang Provincial Innovation Center of Advanced Chemicals Technology, Institute of Zhejiang University - Quzhou, 324000, Quzhou, PR China. Electronic address:
The selective hydrogenation of nitrile compounds represents a pivotal area of research within both industrial and academic catalysis. In this study, we prepared Ni-Cu bimetallic catalysts through a co-deposition-crystallization sequence, aimed at the efficient production of primary and secondary amines. The enhanced selectivity for primary amines is attributed to the downshift of the d-band center of NiCu, which weakens the adsorption of key imine intermediates.
View Article and Find Full Text PDFJ Am Soc Mass Spectrom
January 2025
Department of Chemistry, Bagley Hall, Box 351700, University of Washington, Seattle, Washington 98195-1700, United States.
We report a study of internal covalent cross-linking with photolytically generated diarylnitrile imines of N-terminal arginine, lysine, and histidine residues in peptide conjugates. Conjugates in which a 4-(2-phenyltetrazol-5-yl)benzoyl group was attached to C-terminal lysine, that we call RAAA--K, KAAA--K, and HAAA--K, were ionized by electrospray and subjected to UV photodissociation (UVPD) at 213 nm. UVPD triggered loss of N and proceeded by covalent cross-linking to nitrile imine intermediates that involved the side chains of N-terminal arginine, lysine, and histidine, as well as the peptide amide groups.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
December 2024
Leibniz-Institut für Katalyse, Albert-Einstein-Straße 29a, 18059, Rostock, Germany.
J Colloid Interface Sci
March 2025
School of Chemistry, University of Glasgow, Glasgow G12 8QQ, UK. Electronic address:
Controllable surface modification of nanoparticulate drug delivery vectors is key to enhancing specific desirable properties such as colloidal stability, targeting, and stimuli-responsive cargo release. Metal-organic frameworks (MOFs) have been proposed as potential delivery devices, with surface modification achieved by various bioconjugate "click" reactions, including copper-catalysed and strain-promoted azide-alkyne cycloaddition. Herein, we show that photo-induced nitrile imine-mediated tetrazole-ene cycloaddition (NITEC) can be used to surface-modify tetrazole-appended Zr MOFs with maleimides, and vice versa, with the extent of this traceless surface functionalisation controlled by the length of photoirradiation.
View Article and Find Full Text PDFJ Am Soc Mass Spectrom
January 2025
Department of Chemistry, Bagley Hall, Box 351700, University of Washington, Seattle, Washington 98195-1700, United States.
Peptide conjugates furnished with a 2,5-diaryltetrazolecarbonyl tag at the C-terminal lysine, which we call peptide--K, were found to undergo efficient cross-linking of Asp, Glu, Asn, and Gln residues to transient nitrile-imine intermediates produced by photodissociation and collision-induced dissociation (CID) of the tetrazole ring in gas-phase ions. UV photodissociation (UVPD) at 213 nm achieved cross-linking conversion yields of 37 and 61% for DAAAK--K and EAAAK--K, respectively. The yields for NAAAK--K and QAAAK--K were 29 and 57%, respectively.
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