A one-pot synthesis of constitutionally unsymmetrical rotaxanes using sequential Cuⁱ-catalyzed azide-alkyne cycloadditions

Abstract

A one-pot sequential CuI-catalyzed azide-alkyne cycloaddition (CuAAC) strategy is presented for the synthesis of constitutionally unsymmetrical cyclobis(paraquat-p-phenylene)-based rotaxanes in good yields from simple starting materials. The methodology consists of performing multiple CuAAC reactions to stopper a pseudorotaxane in a stepwise manner, the order of which is controlled through silyl-protection and AgI-catalyzed deprotection of a terminal alkyne. The methodology is highlighted by the synthesis of an amphiphilic branched [4]rotaxane. The methodology increases the ability to access ever more complicated mechanically interlocked compounds to serve in devices as sophisticated and functional molecular machinery. © 2008 Wiley-VCH Verlag GmbH & Co. KGaA,.