Sequence isomerism in [3]rotaxanes

Abstract

We describe a strategy for assembling different macrocycles onto a nonsymmetrical rotaxane thread in a precise sequence. If the macrocycles are small and rigid enough so that they cannot pass each other then the sequence is maintained mechanically, affording stereoisomerism in a manner reminiscent of atropisomerism. The method is exemplified through the synthesis of a pair of [3]rotaxane diastereomers that are constitutionally identical other than for the sequence of the different macrocycles on the thread. The synthesis features the iterative binding of different palladium(II) pyridine-2,6-dicarboxamide complexes to a pyridine ligand on the thread followed by their macrocyclization by ring-closing olefin metathesis. Removal of the palladium(II) from the first rotaxane formed frees the pyridine site to coordinate to a second, different, palladium(II) pyridine-2,6-dicarboxamide unit which, following macrocyclization, provides a multiring rotaxane of predetermined macrocycle sequence.