M. V. Anokhin

Arylation of adamantanamines: VII. Copper(I)-catalyzed N-heteroarylation of adamantane-containing amines with halopyridines

Copper(I)-catalyzed N-heteroarylation of a wide series of adamantane-containing amines with 2-bromo- and 2- and 3-iodopyridines was studied. The corresponding N-pyridyl derivatives were formed in all cases, but iodopyridines were considerably more reactive. The best results were obtained with the catalytic system CuI-2-(2-methyl-1-oxopropyl)cyclohexanone-DMF which ensured up to 90% yield of the target products. The yield of N-pyridyl derivatives also depended on the steric environment of the amino group in the initial adamantane-containing amine. The yield of the heteroarylation products can be considerably increased using excess iodopyridine. The reaction of 2-(adamantan-1-yl)ethanamine with 2,6-dibromopyridine successfully afforded the corresponding diamine, and N,N′-dipyridyl derivatives were obtained in high yields from 2,2′-(adamantane-1,3-diyl)diethanamine.

Palladium-catalyzed amination in the synthesis of aza- and diazacrown trismacrocyclic compounds

Palladium-catalyzed C-N-cross-coupling of N,N′-bis(bromobenzyl) diazacrown compounds with two equivalents of 1-aza-15-crown-5 and 1-aza-18-crown-6 ethers furnished trismacrocyclic compounds with isolated macrocycles. Macrotricyclic cryptands were obtained when diazacrown ethers were used as N-components.

Polystyrene-supported cu(II)-R-Box as recyclable catalyst in asymmetric Friedel–Crafts reaction

The complex of copper(II) trifluoromethanesulfonate with chiral isopropyl bis(oxazoline) ligand (i-Pr-Box) was immobilized on accessible and inexpensive Merrifield resin according to a “click” procedure. The resulting catalyst showed high efficiency and recyclability in the asymmetric Friedel–Crafts alkylation of indole and its derivatives. The catalyst can be recycled five times without appreciable loss in activity and enantioselectivity.

Copper(I)-catalyzed amination of halothiophenes with polyamines

Copper(I)-catalyzed hetarylation of a series of polyamines and of 4,7,10-trioxatridecane-1,13-diamine with halothiophenes has been studied with a view to obtaining the corresponding N,N′-dihetaryl derivatives. The target products can be obtained using both 3-iodothiophene in the presence of CuI/L-proline/EtCN or CuI/N,N-dimethylglycine/EtCN as catalytic system and 3-bromothiophene in the system CuI/2-(2-methyl-1-oxopropyl)cyclohexanone/DMF. The latter system is also suitable for the hetarylation of 4,7,10-trioxatridecane-1,13-diamine with 3-iodothiophene. In some cases, N-(thiophen-3-yl) derivatives have also been isolated.

CuSO4/Al2O3 as a new effective and recyclable catalyst for the arylation of dialkyl phosphites

A new effective recycled catalyst CuSO4/Al2O3, which performs the phosphorylation of aryl halides and bromostyrene, was proposed.