One‐Step Construction of the Shape Persistent, Chiral But Symmetrical Polyimine Macrocycles

A unique combination of structural flexibility, shape persistency and functionality, makes macrocycles and molecular cages as essential molecular entities that have displayed applications that go beyond chemistry. Among macrocycles, the selectively obtained symmetrical (poly)cyclic polyimines have shown great utility in the design of molecules varied in shape and properties. The reversible and thermodynamically controlled cycloimination reaction is governed by configurational and conformational constraints imposed on the intermediate products, ensures a sufficiently high level of preorganization. The high geometrical control over the macrocycle structure has profound effect on their assembly mode. In this Account, we were interested in showing how the structure of small building blocks affects the structure of macrocyclic product and further, how influenced the association mode of the given macromolecule. The latter is of primarily importance in supramolecular and in material chemistry. Hugo Schiff legacy. Discovered in XIX century the imination reaction in the modern manner provides very complex products from structurally predisposed substrates. The relatively simple building blocks, namely diamines and di‐ or trialdehydes have been used to the synthesis of highly symmetrical (poly)cyclic molecules. The DCC‐based, thermodynamically controlled cycloiminations allowed the obtaining specific products with high, often quanitative yields.