Palladium‐Catalyzed Arylation of Linear and Cyclic Polyamines

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.

Chemoselectivity and the Curious Reactivity Preferences of Functional Groups

“…In 2005, Beletskaya et al reported that selective monoarylation of the primary amine 58 can be achieved with 1,4-dibromobenzene 59 to give 60 in high yield despite the presence of an unprotected secondary amine (Scheme 22). [41] In 2007, Rouden and co-workers observed the opposite trend with cyclic diamine 61, [42] namely selective arylation of the secondary amine occurred. A ligand screen revealed that two factors control the selectivity for primary versus secondary amine arylation: the ring size and the rate of reductive elimination, the latter of which can be modulated by the choice of ligand.…”

Pd-Сatalyzed Amination for the Synthesis of Macropolycycles Comprising Cyclen, Cyclam and Naphthalene Moieties

“…It was surprising because 1-and 2-bromonaphthalenes are known to be very active substrates in Pd-catalyzed amination reactions. [29][30][31] This fact may be explained by the presence of the tetraazamacrocyclic fragment which competes with the phosphine ligand in the coordination of Pd(0) partially removing it from the catalytic cycle.…”

Copper‐Catalyzed Arylation of Oxadiamines and Polyamines

“…The Pd-catalyzed arylation of di-and polyamines was extensively studied by us previously, and excellent selectivity for primary amino group arylation in the presence of secondary amino groups was demonstrated. [33] Pd-catalyzed diarylation of 1,3-diaminopropane and N-(3-aminopropyl)-1,3-diaminopropane was conducted using 4-bromobiphenyl and 1-bromonaphthalene, and the reaction produced N,NЈ-diaryl derivatives in 75-92 % yields. In contrast, copper-catalyzed arylation of diamines has not yet been investigated in detail, and there are few reports in literature on the monoarylation of linear diamines [34] or the diarylation of 1,2-diaminocyclohexane.…”