Doubly chiral pseudopeptidic macrobicyclic molecular cages: Water-assisted dynamic covalent self-assembly and chiral self-sorting

•Bioinspired dynamic covalent self-assembly of pseudopeptidic macrobicycles •Solvent-dependent self-sorting outcome: from polymers to cryptand-like cages •Strong helical chirality induction governed by α-C the pseudopeptides •Supramolecular water encapsulation leading high-fidelity homochiral Taking advantage chemistry approach, four different were synthesized condensation tripodal with 4,4′-biphenyldicarboxyaldehyde. Whereas undesired products polymeric nature obtained in polar solvents, [3+2] cryptand-type macrobicyclic architectures excellent yields using chloroform as solvent, even at relatively high concentrations. The presence two encapsulated molecules may provide a positive template effect low polarity medium. final display combination types chirality: d,l due asymmetric centers and P,M chirality. helicity found for all enantiomerically pure molecular indicates strong α-C. Besides, properties chiral have been studied, resulting homo-self-sorting. DFT calculations point out that outcome also be direct result within cavity.