An overview of the latest developments in the metal-free synthesis of non-benzo-fused N-functionalized and NH-1,2,3-triazoles is provided in this feature article. Synthetic studies that appeared from 2016 until August 2020 are organized according to a wide-ranging classification, comprising oxidative and eliminative azide-dipolarophile cycloadditions, diazo transfer reactions and N-tosylhydrazone-mediated syntheses. The newly developed methods constitute a significant contribution to the field of 1,2,3-triazole synthesis in terms of structural variation via either the exploration of novel reactions, or the exploitation of existing methodologies.

A [P₄₄₄₁₄][Cl]–NaCl–H₂O IL-based aqueous biphasic system shows promising results for the separation of cobalt(ii) and nickel(ii) by homogeneous liquid–liquid extraction.

A new N-atom donor extractant 2,9-bis(1-(2-ethylhexyl)-1H-1,2,3-triazol-4-yl)-1,10-phenanthroline (EH-BTzPhen) was synthesized and used in solvent extraction studies to separate the trivalent minor actinide americium(III) and curium(III) from europium(III), representing fission product lanthanides. The extractant was found to be soluble in 1-octanol and in the Aliquat-336 nitrate ([A336][NO₃]) ionic liquid diluent, but insoluble in n-dodecane. The [A336][NO₃] is a fully incinerable room temperature ionic liquid, and has a higher flash point than aliphatic diluents such as 1-octanol. The EH-BTzPhen proved to be effective for selective minor actinide extraction only in combination with 2-bromohexanoic acid synergist when 1-octanol was used as a diluent (SF _Am/Eu > 200). The change of the diluent from 1-octanol to Aliquat-336 nitrate allowed selective An(III) extraction from low acidity feed solutions without the need of a synergist (SF _Am/Eu ~ 70 and SF _Am/Cm ~ 1.9–2.2). The phase transfer kinetics of the ligand-metal complexes is however very slow at 22°C in the case of both solvents. With this newly synthesized extractant, the achieved SF _Am/Cm was comparable to the values achieved with the established CyMe₄BTBP and CyMe₄BTPhen extractants.

In recent years, several organocatalytic/metal-free synthetic pathways towards 1,2,3-triazoles have been reported. One of them is a general metal-free route towards the synthesis of 1,5-di- or fully-substituted 1,2,3-triazoles, designed by our group and named the ‘triazolization’ reaction of ketones. Limitations of this route were encountered in reactions with more activated ketones, where the corresponding 1-(4-nitrophenyl)-1,2,3-triazole was found back as the major product. Interestingly, three different triazoles are formed when 1,3-diphenylacetone is used as the ketone. In the present work, 1,3-diphenylacetone was used as a model substrate to investigate the chemoselectivity of our metal-free route under different reaction circumstances. This led to the conclusion that the formation of the desired 1,2,3-triazole is favored in apolar solvents, at high temperatures, and in the presence of acetic acid. By using one equivalent of acetic acid, previously inaccessible fully decorated 1,2,3-triazoles can be synthesized from simple α-arylketones in moderate to high yields.