Symmetry-driven diastereoselective functionalization of simple trianglamine.

We have found that derivatization of the trianglamine macrocycle by aliphatic aldehydes leads selectively to one of the two possible diastereomeric aminal products. X-ray analysis, NMR measurements and DFT calculations pointed to the product possessing a higher symmetry.

Sterically Crowded Trianglimines-Synthesis, Structure, Solid-State Self-Assembly, and Unexpected Chiroptical Properties.

The chiral, triangular-shape hexaimine macrocycles (trianglimines), bearing bulky alkynyl or aryl substituents were synthesized and studied by means of experimental and theoretical methods. The macrocyclization reactions are driven by the extraordinary stability of the trianglimine ring and provided products with high yields. Electrostatic repulsion between imine nitrogen atoms and the substituents forced an anti conformation of the aromatic linkers. Although the DFT-optimized structure of 7 is D3 symmetrical, in the crystal, the macrocycle adopts a bowl-like molecular shape. The macrocycle self-assembles into tail-to-tail dimers by mutual interdigitation of aromatic moieties. In contrast, macrocycle 8 adopts a rigid pillararene-like conformation. The nature of the substituent significantly affects the electronic properties of the linker. As a result, unexpectedly high exciton Cotton effects are observed in the electronic circular dichroism (ECD) spectra. The origin of these effects was subject of an in-depth study.