Boronic ester-templated pre-rotaxanes as versatile intermediates for rotaxane endo-functionalisation

We report on the synthesis of [2]rotaxanes from vicinal diols through dynamic covalent boronic ester templates, as well as the use of the boronic ester for rotaxane post-functionalisation. A boronic acid pincer ligand with two alkene-appended arms was condensed with a linear diol-containing thread, and ring-closing metathesis established a pre-rotaxane architecture along with a non-entangled isomer. Advanced NMR spectroscopy and mass spectrometry unambiguously assigned the isomers and revealed that the pre-rotaxane was in equilibrium with its hydrolyzed free [2]rotaxane form. The boronic ester handle in the pre-rotaxane could be synthetically addressed in a multitude of ways to obtain different endo-functionalised [2]rotaxanes, including with direct oxidation reactions, protodeboronation, functional group interconversions and Pd-catalysed cross-couplings.