Innovative Methodologies for the N-Protection of N-Alkylimidazole Groups:  Application to the First Synthesis of a Water-Soluble Calix[6]arene Presenting Three Ammonium Substituents at the Large Rim and Three Neutral N-Donors at the Small Rim

The first synthesis of a cationic amphiphile calixarene ligand, which bears three neutral imidazole donors on one side of the hydrophobic cone and three quaternary ammonium substituents on the other side, is reported. The synthetic strategy relies on two key steps: (i) the “small rim-directed” selective ipso-nitration at the large rim and (ii) a protection−deprotection sequence of the N-alkylimidazole groups, for which two equally efficient novel methods (coordination to Zn(II) or to a cyanoborane) are presented.