0000000000274052
AUTHOR
Alla G. Bessmertnykh
Cover Picture: Palladium-Catalyzed Arylation of Linear and Cyclic Polyamines (Eur. J. Org. Chem. 2/2005)
The cover picture shows the model structures of four compounds among the hundred of arylated linear and cyclic polyamines prepared by palladium-catalyzed coupling of mono- and dihalogenoarenes with various aliphatic or aromatic polyamines. The reaction is strongly dependent on the nature and the concentration of the catalytic system, as well as the nature of the base. The competitive reaction between primary and secondary amines and the monoamination of dihalobenzenes have also been detailed in the article by R. Guilard et al. on p. 261 ff. In the following article by the same authors on p. 281 ff, the method has been applied to the synthesis of numerous nitrogen- and oxygen-containing macr…
Palladium-catalyzed amination of aryl dibromides with secondary amines: synthetic and mechanistic aspects
Abstract Diaminobenzenes are obtained starting from m- and p-dibromobenzenes and secondary amines in the presence of Pd(dba)2/P(o-tolyl)3and sodium tert-butoxide in moderate to good yields. Reductive dehalogenation of aryl dibromides is a major side reaction under these conditions. The study of this reaction has shown that the formation of reductive dehalogenation products occurs according to two independent ways. The first one proceeds via the well-known β-hydride elimination from amido-coordinated palladium complexes. The second one involves the formation of hydrido palladium complexes from amino-coordinated derivatives. Although our results do not allow us to propose a detailed mechanist…
Palladium-Catalyzed Arylation of Linear and Cyclic Polyamines.
Synthetic protocols for the palladium-catalyzed arylation of various linear and cyclic polyamines and polyoxapolyamines has been worked out. Pd(0) and Pd(II) complexes with such phosphine ligands as dppf, BINAP, PPF-OMe, P(tBu) 3 , 2-ditert-butylphosphino- 1,1'-biphenyl have been explored in the catalytic amination reactions. Monoamination of chloro-, bromo-, and iodoarenes with di-, tri-, and tetraamines have been carried out, condi- tions for di- and polyarylation of linear polyamines have been elaborated. Successful aryla- tion of 1,4,7,10-tetraazacyclododecane (cyclene) and 1,4,8,11-tetraazacyclotetradecane (cy- clam) have been conducted. Intramolecular diamination of dihaloarenes such …
Palladium-catalyzed synthesis of aryl-substituted polyamine compounds from aryl halides
The reaction of polyamines having primary amino groups and 1,2-diaminoethane and/or 1,3-diaminopropane fragments with aryl bromides or iodides in the presence of sodium tert-butoxide and (dppf)PdCl2 (dppf = 1,1′-bis(diphenylphosphino)ferrocene) proceeds selectively leading to monoaryl-substituted derivatives of polyamine. This reaction provides a convenient method of arylation of di-, tri- and tetraamine compounds. The Pd-catalyzed reactions of 1,3-diaminopropane and 3,3′-diaminodipropylamine with more reactive 1-bromonaphthalene can be used for the preparation of sym-dinaphthyl derivatives of these amines.
Palladium-Catalysed Amination of 1,8- and 1,5-Dichloroanthracenes and 1,8- and 1,5-Dichloroanthraquinones
Diamino derivatives of anthracene and anthraquinone have been synthesised by palladium-catalysed coupling of 1,8-dichloroanthracene and 1,8-dichloroanthraquinone with a wide range of aliphatic and aromatic primary and secondary amines. The use of polyamines gave rise to a large number of new nitrogen- and oxygen-containing macrocycles incorporating anthracene or anthraquinone moieties. The method has also been employed for the preparation of bismacrocycles in which two cyclam or azacrown units are linked together by an anthracene bridge through C(sp2)−N bonds. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005)