Palladium-catalyzed arylation of linear and cyclic polyamines
I. P. Beletskaya and A. D. Averin
Department of Chemistry, Lomonosov Moscow State University,
Leninskie Gory, Moscow 119992, Russia
Abstract: 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, conditions for di- and polyarylation of linear polyamines
have been elaborated. Successful arylation of 1,4,7,10-tetraazacyclododecane
(cyclene) and 1,4,8,11-tetraazacyclotetradecane (cyclam) have been conducted.
Intramolecular diamination of dihaloarenes such as 1,2-dibromobenzene,
2,6-dichlorobromobenzene, 1,3-dibromobenzene, 1,8-dichloroanthracene,
1,8-dichloroanthraquinone, 1,5-dichloroanthracene, and 1,5-dichloroanthraquinone
afforded corresponding polyazamacrocycles containing arene moieties.
For the first time, a convenient one-pot synthesis of the face-to-face
arranged bismacrocyclic systems has been carried out.
*Plenary lecture presented at the XVII Mendeleev Congress
on General and Applied Chemistry, Kazan, Tatarstan, Russia, 21 -26 September
2003. Other presentations are published in this issue, pp.
1605-1798.
