Chemistry with Roataxanes: Intra- and Intermolecularly Covalently Linked Rotaxanes

The direct introduction of sulfonamide units (cf. 9) into carboxamide-based rotaxanes allows us to intramolecularly bridge the “wheel” and the “axle” of such species for the first time as is shown by the bridged bissulfonamide rotaxane 11. Due to its stronger acidity the SO2-NH proton can be selectively abstracted by mild bases even in the presence of CO.NH and then be substituted by treatment with suitable iodo compounds. This leads intramolecularly to 11 (71% yield) and intermolecularly to bis[2]rotaxane 16 (76% yield). The iodo-substituted rotaxane 15 isolated as a remarkably stable byproduct offers a new synthetic potential demonstrated by the preparation of 16.