Macrocycles & shape persistent organic cages

Large-ring, non-collapsible chiral heterocycles are of considerable interest for their promising applications as ligands, organocatalysts and scaffolds for biomimetic and nanopatterning purposes. Efficient assembly of a macrocycle or a organic cage still represents a formidable synthetic challenge.

In our laboratory we developed a method for one-step synthesis of chiral macrocycles and cages by cyclization of vicinal diamines with appropriate carbonyl compound. When racemic diamine is used, the macrocycle/macrocage formation is highly stereoselective and yield racemic mixtures that contain homochiral products with absolute configuration of either all-R or all-S at the stereogenic centres. The vase-like macrocycles form dimers that are assembled into higher-order structures in the solid state as well as in the solution. The formation of these dimers is accomplished by enantioselective self-recognition of chiral macrocycle units.

Figure 1

The macrocyclic or macrocage polyimine products can be easy transform to chiral poliamines with high yield and further functionalized. The polyimine/polyamine macrocycles and macrocages are used as chiral selectors, ligands, catalysts and materials with predetermined properties.