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

Palladium-Catalyzed Amination of Dichloroquinolines with Adamantane-Containing Amines

“…These better results compared to the reactions with 2,8-dichloroquinoline can be attributed to a lower reactivity of the chlorine atom in the position 4 due to steric reasons and to the absence of the possible side reactions like N,N -diarylation. These results are in a good correspondence with our recent observations of the catalytic amination of 2- and 4-chloroquinolines [ 40 ]. The diamination of 4,8-dichloroquinoline with the most hindered amine 1d is possible when using DavePhos ligand (entry 8), whereas in the presence of BINAP the reaction gave only the monoamination product 5d almost in the same yield as it was with one equivalent of amine 1d (entry 7).…”

“…To compare, in the compound 2a the protons of the CH 2 N group are observed at 3.7 ppm and corresponding carbon atom possesses the chemical shift 42.0 ppm. The downfield shift of both protons and carbon atoms in CH 2 NQuin 2 fragment compared to CH 2 NHQuin is very characteristic [ 40 ] and verifies the structure of the compound 3 . Additional support is provided by a pronounced downfield shift of the H3, H3' protons of the quinolinyl moieties in compound 3 (7.47 ppm compared to 6.67 ppm in N -monoaryl derivative 2a ).…”

“…Taking all these facts into consideration and in view of our interest in the Buchwald-Hartwig amination of heteroaryl halides [ 37 , 38 , 39 , 40 ], we decided to study the Pd-catalyzed amination reactions of isomeric dichloroquinolines with selected adamantane-containing amines, which differ in the steric hindrance at the amino group, and to determine the best conditions for the selective mono- and diamination of these hetaryl dichlorides.…”

Mono- and Diamination of 4,6-Dichloropyrimidine, 2,6-Dichloropyrazine and 1,3-Dichloroisoquinoline with Adamantane-Containing Amines

“…MALDI-TOF mass spectra revealed the presence of the oligomers comprising 2-3 pyrimidine units combined with 3 or 4 amine fragments which could not be separated by column chromatography (e.g., (4a) 3 Het 2 , [M + H] + 738.48 and (4a) 4 Het 3 , [M + H] + 1009.59, Scheme4). N,N-diheteroarylation was observed to be typical in the amination of 2-halosubstituted 6-membered heterocycles (pyridine and quinoline)[32,33,39,40].…”