CC BY-NC-ND 4.0 · Synthesis 2021; 53(24): 4527-4548
DOI: 10.1055/a-1665-4650
review

Covalently Templated Syntheses of Mechanically Interlocked Molecules

Milo D. Cornelissen
,
Simone Pilon
,
Jan H. van Maarseveen
The authors would like to thank the Nederlandse Organisatie voor Wetenschappelijk Onderzoek (Netherlands Organization for Scientific Research, NWO-CW, ECHO grant number 711.012.007 to J.v.M).


This review is dedicated to the 70th birthday of Professor Ben L. Feringa

Abstract

Mechanically interlocked molecules (MiMs), such as catenanes and rotaxanes, exhibit unique properties due to the mechanical bond which unites their components. The translational and rotational freedom present in these compounds may be harnessed to create stimuli-responsive MiMs, which find potential application as artificial molecular machines. Mechanically interlocked structures such as lasso peptides have also been found in nature, making MiMs promising albeit elusive targets for drug discovery. Although the first syntheses of MiMs were based on covalent strategies, approaches based on non-covalent interactions rose to prominence thereafter and have remained dominant. Non-covalent strategies are generally short and efficient, but do require particular structural motifs which are difficult to alter. In a covalent approach, MiMs can be more easily modified while the components may have increased rotational and translational freedom. Both approaches have complementary merits and combining the unmatched efficiency of non-covalent approaches with the scope of covalent syntheses may open up vast opportunities. In this review, recent covalently templated syntheses of MiMs are discussed to show their complementarity and anticipate future developments in this field.

1 Introduction

2 Tetrahedral Templates

2.1 A Carbonate Template for Non-Rusty Catenanes

2.2 All-Benzene Catenanes on a Silicon Template

2.3 Backfolding from Quaternary Carbon

3 Planar Templates

3.1 Rotaxanes Constructed in a Ring

3.2 Hydrindacene as a Dynamic Covalent Template

3.3 Templating on Tri- and Tetrasubstituted Benzenes

4 Conclusion



Publication History

Received: 30 August 2021

Accepted after revision: 17 September 2021

Accepted Manuscript online:
08 October 2021

Article published online:
15 November 2021

© 2021. The Author(s). This is an open access article published by Thieme under the terms of the Creative Commons Attribution-NonDerivative-NonCommercial-License, permitting copying and reproduction so long as the original work is given appropriate credit. Contents may not be used for commercial purposes or adapted, remixed, transformed or built upon. (https://creativecommons.org/licenses/by-nc-nd/4.0/)

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