Stepwise Functionalization of a Pillar[5]arene-Containing [2]Rotaxane with Pentafluorophenyl Ester Stoppers

Detailed investigations into the stepwise bis-functionalization of a pillar[5]arene-containing rotaxane building block have been carried out. Upon a first stopper exchange, the pillar[5]arene moiety of the mono-acylated product is preferentially located close to its reactive pentafluorophenyl ester stopper, thus limiting the accessibility to the reactive carbonyl group by the nucleophilic reagents. Selective mono-functionalization is thus very efficient. Introduction of a second stopper is then possible to generate dissymmetrical rotaxanes with different amide stoppers. Moreover, when dethreading is possible upon the second acylation, the pillar[5]arene plays the role of a protecting group allowing the synthesis of dissymmetrical axles that are particularly difficult to prepare under statistical conditions. Finally, detailed conformation analysis of the rotaxanes revealed that the position of the pillar[5]arene moiety on its axle subunit is mainly governed by polar interactions in nonpolar organic solvents, whereas solvophobic effects play a major role in polar solvents. The pillar[5]arene as a protecting group. Selective mono-functionalization of a rotaxane building block is very efficient owing to steric effects limiting the access of the nucleophilic reagents to the second reactive carbonyl group. Introduction of a second stopper is then possible to generate dissymmetrical rotaxanes or axles in high yields.image