The formation of chiral non-racemic perazamacrocyles containing three or
more nitrogen atoms in the form of identical of different functionalities can be achieved
by diverse methods, among which the reaction of primary amines with carbonyl
compounds to form polyimino macrocycles. The rigidity and restricted flexibility of the
reaction partners is generally required to get success in cyclization. Alternatively,
cyclization can be favored by using a metal template. The carbon stereocenters in the
formed macrocycle are usually present in the starting nitrogen-containing reagent, e.g.
amine, diamine, α-aminoacid and their derivatives. Preformed imines can be also used
as precursor of macrocyclic rings. Intrinsically chiral porphyrins, lacking carbon
stereocenters, and bridged bis(macrocyclic) compounds incorporating porphyrins
(strapped porphyrins) and analogous macrocycles have been also surveyed. Chiral
perazamacrocycles and their metal complexes have found applications in the fields of
biomedical research, diagnosis, anion sensing, molecular recognition, enantiomeric
discrimination, asymmetric catalysis, and material chemistry.
Keywords: Aldol condensation, amines, asymmetric synthesis, bridged
macropolycycles, chiral perazamacrocycle, cyclization, cyclocondensation,
cyclopolypeptides, diastereoselective reduction, enantioselective catalysis,
enantioselective recognition, epoxidation, ex-chiral pool synthesis, guanidinium
macrocycles, Henry reaction, hydrazones, imines, organometallic reaction, metal
complexes, metal ion coordination, material chemistry, molecular recognition,
nitrogen ligands, nucleophilic substitution, perazamacrocycles, pharmaceutical,
porphyrins, receptors, reductive coupling, reduction, rhombimines, supramolecular
chemistry, template-aided macrocyclization, trianglamines, trianglimines,
tropocoronands.
