Synthesis of polyaza macrocycles by palladium-catalyzed amination of 1,2-dibromobenzene and 2-bromo-1,3-dichlorobenzene

Averin, Alexei D.; Shukhaev, Anton V.; Buryak, А. К.; Beletskaya, I. P.

doi:10.1134/s1070428009090085

Cited by 6 publications

(4 citation statements)

References 21 publications

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“…These data show that copper-catalyzed arylation of polyamines is more sensitive to steric factors than palladium-catalyzed reactions because previously we showed that facile amination of o-dibromobenzene and 2,6-dichlorobromobenzene occurred. [39] The N 1 ,N 4 -diarylation of tetraamine 1a with electronrich p-methoxyiodobenzene proceeded normally, and the target product 29 was isolated in 52 % yield (Table 6, entry 5). In this reaction other isomeric diaryl and monoaryl compounds were also obtained as inseparable fractions.…”

Section: Resultsmentioning

confidence: 99%

Copper‐Catalyzed Arylation of Oxadiamines and Polyamines

Anokhin¹,

Averin²,

Beletskaya³

2011

Eur J Org Chem

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Copper‐catalyzed arylation of oxadiamines and polyamines aimed at the synthesis of N,N′‐diaryl derivatives using bromo‐ and iodoarenes was studied. Conversion of the starting compounds, selectivity of the arylation of primary amino groups in the presence of the secondary amino groups, and the yields of target products were shown to be strongly dependent on the nature of the oxadiamines and polyamines, aryl halides, and halogen atom, as well as on reaction conditions such as ligand, solvent, and base applied. Reliable catalytic systems were found for each type of starting amine and aryl halide affording the highest possible yields of the products of N,N′‐diarylation (65–96 %).

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Section: Resultsmentioning

confidence: 99%

Copper‐Catalyzed Arylation of Oxadiamines and Polyamines

Anokhin¹,

Averin²,

Beletskaya³

2011

Eur J Org Chem

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“…t BuONa as a base. Usually, the Pd-catalyzed diamination of the ortho -dihalogenoarenes is hindered because the introduction of the first amino group decreases the reactivity of the resting halogen atom [ 60 , 61 ]. In our case, the application of 4 equiv.…”

Section: Resultsmentioning

confidence: 99%

“…The much higher reactivity of the primary amino groups than that of the secondary amino groups in the Pd-catalyzed amination reactions is well established and ensures the formation of the corresponding macrocycles [ 62 ]. However, polyamines are better chelators for palladium than oxadiamines and can lead to a decrease in the efficiency of the process and diminish the yield of the target products [ 61 ].…”

Section: Resultsmentioning

confidence: 99%

Polyoxa- and Polyazamacrocycles Incorporating 6,7-Diaminoquinoxaline Moiety: Synthesis and Application as Tunable Optical pH-Indicators in Aqueous Solution

et al. 2023

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Synthetic approach to fluorescent polyaza- and polyoxadiazamacrocycles comprising a structural fragment of 6,7-diamino-2,3-diphenylquinoxaline has been elaborated using Pd-catalyzed amination providing target compounds in yields up to 77%. A series of nine novel N- and N,O-containing macrocyclic ligands differing by the number of donor sites and cavity size has been obtained. These compounds possess well-pronounced fluorescent properties with emission maxima in a blue region in aprotic solvents and high quantum yields of fluorescence, while in proton media, fluorescence shifts towards the green region of the spectrum. Using macrocycles 5c and 5e as examples, we have shown that such compounds can serve as dual-channel (colorimetric and fluorimetric) pH indicators in water media, with pH transition point and response being dependent on the macrocycle structure due to different sequences of protonation steps.

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“…Because of steric and electronic hindrances created by the amino group introduced first, o-dibromobenzene gave rise to macrocycles in lower yields (12-25%) [78]. Using 2,6-dichlorobromobenzene having an additional electron-withdrawing substituent, we succeeded in raising the yield by 10-15% [79] (Scheme 11). The highest yield (56%) of macrocyclic compound was obtained in the reaction with m-dibromobenzene [80] (Scheme 12).…”

Section: Cyclic Oligomersmentioning

confidence: 91%

Palladium-catalyzed amination in the synthesis of polyazamacrocycles

et al. 2010

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The review describes palladium-catalyzed amination of acyclic di-and polyamines with aryl halides with a view to reveal general relations holding in this process. Conditions for the synthesis of macrocycles via catalytic diamination of 1,2-and 1,3-dibromobenzenes, 1,3-dichloro-2-bromobenzene, 2,6-and 3,5-dibromopyridines, 3,3′-and 4,4′-dibromobiphenyls, 2,7-dibromonaphthalene, 1,8-and 1,5-dichloroanthracene, 1,8-and 1,5-dichloroanthraquinones, and bis(haloaryl) derivatives of cyclen, cyclam, and cholanediol are discussed. The possibility for palladium-catalyzed arylation of cyclic polyamines has been demonstrated. Specificity of macrocyclization processes and relations between the yield of macrocycles and the nature of initial compounds are considered, and data on the synthesis of cyclic dimers are given. Applications of polyazamacroheterocycles as optical sensors for metal cations are described using as examples macrocyclic compounds derived from 1,8-disubstituted anthraquinone.

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Synthesis of polyaza macrocycles by palladium-catalyzed amination of 1,2-dibromobenzene and 2-bromo-1,3-dichlorobenzene

Cited by 6 publications

References 21 publications

Copper‐Catalyzed Arylation of Oxadiamines and Polyamines

Copper‐Catalyzed Arylation of Oxadiamines and Polyamines

Polyoxa- and Polyazamacrocycles Incorporating 6,7-Diaminoquinoxaline Moiety: Synthesis and Application as Tunable Optical pH-Indicators in Aqueous Solution

Palladium-catalyzed amination in the synthesis of polyazamacrocycles

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