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The Chan–Lam reaction conditions were optimized for the synthesis of N-aryl derivatives of adamantane-containing amines. A number of adamantane-containing amines and diamines with different steric hindrances at the primary amino groups were reacted with p-tolylboronic acid under the optimized conditions [0.1 M solution of amine in MeCN, p-tolylboronic acid (2 equiv), DBU (2 equiv), copper(II) acetate (20 mol %), 25°C, 24 h]. The reactivity of the amines was found to strongly depend on their structure, and the maximum yield of the target products reached 74% from the monoamines and 66% from the diamines. [ABSTRACT FROM AUTHOR]

N-(Het)arylation of adamantane-containing amines with halonaphthalenes and haloquinolines catalyzed by either CuI or copper nanoparticles with an average size of 25 nm in the presence of 2-isobutyrylcyclohexanone, rac-BINOL, and l-proline as a ligand and Cs2CO3 as a base in DMSO at 110 °C was studied. The reactions proceed smoothly with 2-iodonaphthalene and 6-iodoquinoline, the possibility of successful reactions with 6- and 3-bromoquinolines was also shown. In the case of 1-bromonaphthalene, 5- and 8-bromoquinolines, only Pd-catalyzed amination can provide the high yields of the products. An alternative possibility of C(sp2)—N bond formation was studied employing the Chan—Lam reaction with of 2-naphthaleneboronic acid and pinacolates of 6- and 3-quinolineboronic acids. [ABSTRACT FROM AUTHOR]

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. [ABSTRACT FROM AUTHOR]

The N-heteroarylation of n-octylamine and adamantane-containing amines with 2-iodopyridine and 2-bromopyridine and its fluorinated derivatives under the catalysis of CuI and copper nanoparticles in DMSO in the presence of various ligands was studied. 2-Isobutyrylcyclohexanone was found to be the most efficient ligand in the reactions catalyzed by CuI. In the reactions catalyzed by copper nanoparticles, 2-isobutyrylcyclohexanone or l-proline turned to be most active. The yields of the reactions catalyzed by copper nanoparticles were better than or equal to those in the CuI-catalyzed processes. The possibility of nanocatalyst recycling was studied, and its reuse in 6 cycles without loss of activity was demonstrated. [ABSTRACT FROM AUTHOR]

N-Arylation of n-octylamine and adamantane-containing amines with iodobenzene and its deriva-tives has been performed in DMSO using copper(I) iodide and copper nanoparticles in the presence of various ligands as catalysts. In all cases, 2-isobutyrylcyclohexanone turned out to be the most efficient ligand, and higher yields of the arylation products were obtained in the presence of copper nanoparticles. The nanocatalyst can be recycled 9 times without significant loss of yield. [ABSTRACT FROM AUTHOR]