Calix[5]arene Through-the-Annulus Threading of Dialkylammonium Guests Weakly Paired to the TFPB Anion

Through-the-annulus threading of calix[5]arene penta-O-ethers by dialkylammonium cations coupled to the loosely coordinating superweak TFPB- anion has been achieved. H-1 NMR titration data show that preorganization of the calix[5]arene scaffold leads to great thermodynamic stability of the pseudorotaxane complexes as well as to a favorable threading kinetic. Thus, calix[5]arene 1c, bearing tert-butyl groups at the wide rim, was threaded by all of the cations under study (with the exception of the dibenzylammonium 2b(+)) more tightly than the other derivatives under investigation (K-a's up to 2.02 +/- 0.2 x 10(5) M-1) because of its preorganized cone conformation. According to DFT calculations, van der Waals interactions between the tert-butyl groups of 1c and the alkyl chain of the cationic axle are likely responsible for the remarkable stability observed. The threading of the calix[S]arene wheels with the asymmetric pentylbenzylammonium axle 2c(+) led to the toposelective formation of the endo-pentylpseudorotaxane stereoisomer in agreement with the known endo-alkyl rule. Owing to the steric hindrance of the axle phenyl group, the threading of the guest was seen to occur in a unidirectional fashion through the calixarene narrow rim.