We report a chiral deep cavitand receptor based on calix[5]arene
stabilized by a cooperative network of hydrogen bonds and having a
highly flexible structure. The cavitand displays enantioselective
molecular recognition with a series of chiral quaternary ammonium
salts, providing unprecedented stability ratios between the corresponding
diastereomeric host–guest complexes. Molecular dynamics simulations
corroborate the higher flexibility of the new host and the emergence
of superior induced-fit behavior with regards to resorcin[4]arene
derived self-folding cavitands.