SummaryThe Cu(I)-catalyzed N,N’-diarylation of natural diamines and polyamines such as putrescine, cadaverine, spermine, spermidine and their homologues is described. Aryl iodides bearing electron-donating and electron-withdrawing groups have been employed in the study. The CuI/2-(isobutyryl)cyclohexanone/DMF catalytic system has found to be more efficient in the diarylation of diamines and spermine while the CuI/L-proline/EtCN system proved to be preferable for the diarylation of other tri- and tetraamines like spermidine, norspermidine and norspermine.
CuI‐Catalyzed amination of 2‐bromo‐, and 2‐, 3‐, and 4‐iodopyridines with tri‐ and tetraamines aimed at the synthesis of N,N′‐diheteroaryl derivatives was studied. A strong dependence of the product yields on the nature of starting compounds and the ligand used was observed. The increase in the number of ethene‐1,2‐diamine fragments in the polyamine structure led to the increase in the yields of polyheteroarylated compounds, whereas propane‐1,3‐diamine fragments favored the formation of monopyridinyl derivatives and promoted the heteroarylation of the secondary amino groups. 2‐Iodopyridine, as a more reactive compound, readily formed N,N‐diarylated products. The best yields of the target N,N′‐dipyridin‐2‐yl derivatives were 76% in the case of the triamine and 68% in the case of the tetraamine. A comparison of CuI‐ and Pd0‐mediated heteroarylation of polyamines was also presented.
Rapid development of the copper-catalyzed amination of aryl halides in the beginning of the 21st century, known as the Renaissance of the Ullmann chemistry, laid foundations for the use of this method as a powerful tool for the construction of the C(sp2)-N bond and became a rival of the Buchwald–Hartwig amination reaction. Various applications of this approach are well-documented in a number of comprehensive and more specialized reviews, and this overview in the form of a personal account of the Cu-catalyzed arylation and heteroarylation of the adamantane-containing amines, and di- and polyamines, covers a more specific area, showing the possibilities of the method and outlining general regularities, considering reagents structure, copper source and ligands, scope, and limitations. The material of the last decade is mainly considered, and recent data on the application of the unsupported copper nanoparticles and possibilities of the Chan-Lam reaction as an alternative to the use of aryl halides are also discussed.
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