Improbable Rotaxanes Constructed From Surrogate Malonate Rotaxanes as Encircled Methylene Synthons

Angew Chem Int Ed Engl. 2023 Oct 26;62(44):e202308974. doi: 10.1002/anie.202308974. Epub 2023 Sep 25.

Abstract

We have developed a new approach for the synthesis of "improbable" rotaxanes by using malonate-centered rotaxanes as interlocked surrogate precursors. Here, the desired dumbbell-shaped structure can be assembled from two different, completely separate, portions, with the only residual structure introduced from the malonate surrogate being a methylene group. We have synthesized improbable [2]- and [3]rotaxanes with all-hydrocarbon dumbbell-shaped components to demonstrate the potential structural flexibility and scope of the guest species that can be interlocked when using this approach.

Keywords: Hydrocarbons; Hydrolysis; Malonate Ester; Rotaxanes; Supramolecular Chemistry.