Cu(I)-catalyzed N,N’-diarylation of natural diamines and polyamines with aryl iodides

Abstract

SummaryThe Cu(I)-catalyzed N,N’-diarylation of natural diamines and polyamines such as putrescine, cadaverine, spermine, spermidine and their homologues is described. Aryl iodides bearing electron-donating and electron-withdrawing groups have been employed in the study. The CuI/2-(isobutyryl)cyclohexanone/DMF catalytic system has found to be more efficient in the diarylation of diamines and spermine while the CuI/L-proline/EtCN system proved to be preferable for the diarylation of other tri- and tetraamines like spermidine, norspermidine and norspermine.

Cu(I)- and Pd(0)-Catalyzed Arylation of Oxadiamines with Fluorinated Halogenobenzenes: Comparison of Efficiency

“…Taking these facts into consideration, one may assume that the reactivity of the oxadiamine 3 is lower than that of 1 and 2, and it helps to obtain better yields in the case of more active aryl iodides, while hampers the reactions with less reactive compounds. This correlates with the data obtained by us earlier with Cu(I)-catalyzed arylation of the polyamines [18]. Alternative Pd(0)-catalyzed arylation (Scheme 1, method B) of the oxadiamines 1-3 was studied using isomeric bromofluorobenzenes as they are preferable compared to iodoarenes.…”

“…During last decade, an important trend in the catalytic organic synthesis has been clearly exhibited, that is, the so-called renaissance of Ullmann chemistry, which is extremely important for the development of new strategies of C-N bond formation [12][13][14][15][16][17]. Our own interest in this field deals with the catalytic arylation and heteroarylation of polyamines [18,19] and adamantane-containing amines and diamines [20,21]. We demonstrated the possibility of successful copper-catalyzed arylation of di-, tri-, and tetraamines as well as of adamantylated amines with fluoroiodobenzenes, (trifluoromethyl) iodobenzenes and fluorine-containing pyridines [18,22,23].…”

“…Our own interest in this field deals with the catalytic arylation and heteroarylation of polyamines [18,19] and adamantane-containing amines and diamines [20,21]. We demonstrated the possibility of successful copper-catalyzed arylation of di-, tri-, and tetraamines as well as of adamantylated amines with fluoroiodobenzenes, (trifluoromethyl) iodobenzenes and fluorine-containing pyridines [18,22,23]. In the previous research, the most efficient catalytic systems for the copper-mediated arylation were found out.…”

Palladium- and Copper-Catalyzed Amination of Halogenophenyl Substituted Porphyrins for the Synthesis of Porphyrin-Azacrown Ethers Conjugates and Evaluation of Their Sensing Properties

“…Having obtained such encouraging results, we have explored the possibility to synthesize a bisporphyrin compound with trioxadiamine linker between two porphyrin moieties and reacted 2 equiv. problematic under Cu I catalysis, [34,35] what is unlikely for Pd 0 -catalyzed diarylation. [36,37] Contrary to the amination of 4-bromophenylporphyrin (1), the Pd 0 -catalyzed reaction of the free di-meso-(4-bromophenyl)porphyrin (9) with excess of propane-1,3-diamine was quite successful and provided 49 % yield of the diamination product 13 (Scheme 2).…”

Recent achievements in copper catalysis for C–N bond formation

“…The attempts to use 2-or 4-chloroquinolines in the same reaction were not as successful and the yields did not surpass 30% due to numerous side reactions. Having acquired enough experience with the copper-catalyzed (hetero)arylation of monoamines, we thoroughly studied the possibilities of the N,N'-diarylation of di-and polyamines [61]. At first, a series of linear diamines was investigated which differ by the number of methylene groups between N atoms (Scheme 10).…”