Copper-catalyzed amination in the synthesis of polyoxadiamine derivatives of aza- and diazacrown ethers

Abstract

Cu(I)-Catalyzed amination of N-(iodobenzyl) substituted azacrown ethers with propane-1,3-diamine and several polyoxadiamines was investigated. In the case of diamine excess and the use of CuI

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

“…At first amino derivatives of N-benzyl substituted crown ethers 25 and 26 were synthesized by the Pd 0 -catalyzed amination of 3-bromobenzyl substituted precursors according to a previously described procedure. [33] Then compounds 25 and 26 were introduced in the second catalytic amination reactions with Zn 3-bromophenylporphyrinate 27 and with di-meso-(4-bromophenyl)porphyrins 9 and 10 (free base and Zn complex, resp.). All reactions were enough successful and provided bismacrocycle 28 or trismacrocycles 29, 30 in comparable 15-20 % yields (Scheme 3).…”

“…Propane-1,3-diamine, dioxa-and trioxadiamines, azacrown ethers, 2-(isobutyryl) cyclohexanone, BINAP, DavePhos, cesium carbonate, sodium tert-butoxide, CuI were purchased from Sigma-Aldrich and used without further purification, Pd(dba) 2 was synthesized according to the method described, [31] halogenophenylsubstituted porphyrines and their Zn complexes 1, 2, 9-12 were synthesized according to a described procedure, [32] synthesis of 3-bromobenzyl derivatives of azacrown ethers 23 and 24 and preparation of diamino derivatives of benzylazacrown ethers 25 and 26 were carried out according to a known method. [33] Dioxane was distilled over NaOH followed by the distillation over sodium under argon, acetonitrile was distilled over CaH 2 , DMF, dichloromethane and methanol were used freshly distilled.…”

Recent Achievements in the Copper-Catalyzed Arylation of Adamantane-Containing Amines, Di- and Polyamines

“…It was shown to be possible to synthesize diamino derivatives of the azacrown ethers using this approach (Scheme 24). The reactions of N-(3-iodobenzyl)-substituted 1-aza-18-crown-6 264 were successfully aminated with the excess of the diamines 200 and 201, and the oxadiamines 218 and 219 to give the corresponding derivatives 265-268 in 50-80% yields [145].…”

Contribution of I. P. Beletskaya in the Twentieth Year Successful Russian-French Cooperation in Catalytic Syntheses

“…[51] Prof. Beletskaya has been deeply interested in the synthesis of immobilized catalysts for their repeated use. The synthetic approach to chiral Brønsted acids like 3,3'-or 6,6'-disubstituted (R)-BINOL phosphoric acids (BINOL=1,1'-binaphthyl-2,2'-diol) bearing either triple bonds or azide groups was developed.…”