A. D. Averin

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 of isomeric dihalobenzenes with 1- and 2-aminoadamantanes

Palladium-catalyzed amination of isomeric bromochloro- and dibromobenzenes with 1- and 2-aminoadamantanes was studied. The best yields of the corresponding monoamination products were obtained in the reactions of 2-aminoadamantane with bromochlorobenzenes. The arylation of 1-aminoadamantane was successful in the presence of donor phosphine ligand. The amination of o- and m-dibromobenzenes was strongly complicated by formation of diamination products. Conditions ensuring predominant formation of the latter were found. The arylation of 2-aminoadamantane was accompanied by oxidation of the initial amine and reduction of aryl halide.

Arylation of adamantanamines: V. Palladium-catalyzed amination of isomeric chloroquinolines with diamines of the adamantane series

Palladium-catalyzed arylation of diamines of the adamantane series with isomeric 2-, 4-, and 6-chloroquinoline was studied, and optimal conditions for the synthesis of the corresponding N,N′-diaryl derivatives were found. N,N-Diarylation products of primary amino groups in the diamines bearing 2-aminoethyl and 4-aminophenyl substituents were readily formed.

Arylation of Adamantanamines: III.* Palladium-Catalyzed Arylation of Adamantane-1,3-diyldimethanamine and 2,2'-(Adamantane-1,3-diyl)diethanamine

Palladium-catalyzed arylation of adamantane-1,3-diyldimethanamine and 2,2′-(adamantane-1,3-diyl) diethanamine with isomeric bromochloro- and dibromobenzenes was studied. The yields of N,N′-diarylation products depend on the initial diamine and dihalobenzene structure. Side reactions were revealed, which reduced the yield of the target products. The arylation of 2,2′-(adamantane-1,3-diyl)diethanamine gives the corresponding N,N′-diaryl derivatives with better yield. The possibility for synthesizing unsymmetrical N,N′-diaryl derivatives of 2,2′-(adamantane-1,3-diyl)diethanamine was demonstrated.

Hydrogenation of α-oxophosphonates with molecular hydrogen catalyzed by palladium on carbon carrier as synthesis procedure for α-hydroxyphosphonates

Hydrogenation with molecular hydrogen of substituted benzoylphosphonic acids ethyl esters provides a convenient preparation method for diethyl [hydroxy(aryl)methyl]phosphonates. Both the palladium on activated carbon and the palladium immobilized in a chitosan matrix applied on a carbon carrier sibunit can be employed as catalysts.

Arylation of adamantanamines: IV. Palladium-catalyzed arylation of amines of adamantane series with isomeric chloroquinolines

Palladium-catalyzed arylation of diverse amines of the adamantane series with isomeric chloroquinolines was investigated. The 2-chloroquinoline is the most reactive, however the best yields of the N-arylation products are most frequently obtained in the reaction with the less reactive 6-chloroquinoline. The applicability of the reaction is limited by the size of the substituent at the amino group. In some instances the noncatalytic amination of chloroquinolines was possible.

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.

Arylation of adamantanamines: II. Palladium-catalyzed amination of dihalobenzenes with adamantylalkanamines

Palladium-catalyzed arylation of various (1-adamantyl)alkanamines with isomeric (ortho, meta, and para) bromochloro- and dibromobenzenes was studied. Optimal catalytic systems were found for the synthesis of mono- and diamination products, and the dependences of their yields on the nature of the initial amine and dihalobenzene and on the amount of base were examined. Side amination products were isolated, and paths of their formation were analyzed.

Palladium-catalyzed amination in the synthesis of nitrogen and oxygen heterocycles containing fragments of cholane and quinoline

By Mitsunobu reaction from 3,24-cholanediol and 2-hydroxy-8-chloroquinoline 24-(8-chloroquinolinyl-2-oxy)cholan-3-ol and 3,24-di(8-chloroquinolinyl-2-oxy)cholane were synthesized. These compounds were brought into reactions of palladium-catalyzed amination with propanediamine, oxaalkane diamines, and N,N′-bis(3-aminopropyl)ethylenediamine to obtain macrocycles of various structures, linear mono- and bis(steroid) derivatives of trioxaalkane diamine, and also cholane bis(oxaalkandiamine) derivative. The dependence was demonstrated of macrocyles and cyclooligomers yield on the polyamine nature. 4-Hydroxy-7-chloroquinoline afforded only 24-(7-chloroquinolinyl-4-oxy)cholan-3-ol.

Synthesis of nitrogen- and oxygen-containing macrocycles by palladium-catalyzed amination of 3,24-bis(6-chloropyridin-2-yloxy)cholane

Abstract3,24-Bis(6-chloropyrdin-2-yloxy)cholane prepared from cholane-3,24-diol by the Mitsunobu reaction was successfully used to synthesize various polyaza macrocycles via palladium-catalyzed amination with linear polyamines. The contribution of side formation of cyclic oligomers was found to depend on the polyamine nature.