Recent Advances in the Synthesis and Applications of Nitrogen-Containing Macrocycles

Abstract

Macrocyclic nitrogen-containing compounds are versatile molecules. Supramolecular, noncovalent interactions of these macrocycles with guest molecules enables them to act as catalysts, fluorescent sensors, chiral or nonchiral selectors, or receptors of small molecules. In the solid state, they often display a propensity to form inclusion compounds. All of these properties are usually closely connected with the presence of nitrogen atoms in the macrocyclic ring. As most of the reviews published so far on macrocycles were written from the viewpoint of functional groups, synthetic methods, or the structure, search methods for literature reports in terms of the physicochemical properties of these compounds may be unobvious. In this minireview, the emphasis was put on the synthesis and applications of nitrogen-containing macrocyclic compounds, as they differ from their acyclic analogs, and at the same time are the driving force for further research.

Unravelling Structural Dynamics, Supramolecular Behavior, and Chiroptical Properties of Enantiomerically Pure Macrocyclic Tertiary Ureas and Thioureas

“…Macrocycles of diverse structures constitute one of the most important general classes of organic compounds of numerous applications in chemistry, biochemistry, and material sciences. − Despite the current progress, the difficulties in synthesis and/or postsynthetic modifications are often recognized as the bottleneck that limits the wide use of macrocycles. , On the other hand, wide availability and possibility of pre- and postsynthetic modifications made the chiral macro- and polycyclic polyaza compounds of periodical structure valuable synthetic targets for creating new (supra)­molecular systems of assumed properties. − Since the first successful synthesis of the basic triangular polyimine (so-called trianglimine ), the numerous applications of these imine-derived, regular-shaped chiral macrocycles as ligands in asymmetric synthesis, molecular receptors, shift reagents in NMR spectroscopy, and light-emitting materials have confirmed the great, but still not fully used, potential of the compounds. − On the contrary, in the case of similar in shape imide-based triangular macrocycles, the number of applications has been considered reverse to difficulties in their synthesis and purification …”

Synthesis of Tetraazamacrocycles by Sequential Palladium‐Catalyzed Allylic Substitution Reactions

“…Other methods such as Nalkylation (strategy 2) and amide bond formation (strategy 3) have been studied, which are irreversible reactions but still result in the formation of oligomeric or polymeric by-products. [10] Palladium-catalyzed allylic substitution is wellestablished for the formation of CÀ C and C-heteroatom bonds. [11] It is theoretically possible to use this method to create tetraazamacrocycles through [2 + 2] allylic substitutions between allylic diol derivatives and diamines, as shown in Figure 1B.…”

“…However, due to the reversible nature of the condensation reactions, different macrocyclic products can be formed, including [1+1], [2+2], [3+3], and polymeric imines, making it challenging to achieve specific conditions for the [2+2] condensation. Other methods such as N ‐alkylation (strategy 2) and amide bond formation (strategy 3) have been studied, which are irreversible reactions but still result in the formation of oligomeric or polymeric by‐products [10] …”

Imine- and Amine-Type Macrocycles Derived from Chiral Diamines and Aromatic Dialdehydes

“…The field of extended macrocycles and their complexes has already been the subject of several review articles, e.g., references [1][2][3][4][5][6][7][8][9][10][11][12][13][14]. In this minireview, extended macrocyclic imines, which are the products of the condensation reactions of aromatic dialdehydes with chiral diamines, such as 1,2-trans-diaminocyclohexane (DACH) or 1,2-diphenylethylenediamine (DPEN), as well as the corresponding amine macrocycles, will be described.…”