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DOI: 10.1055/s-0040-1707125
No, Not That Way, the Other Way: Creating Active Sites in Self-Assembled Host Molecules
RJH would like to thank the National Science Foundation, Division of Chemistry (CHE-1151773 and 1708019) for funding of all these projects, as well as the UC Riverside Center for Catalysis.Publication History
Received: 13 April 2020
Accepted after revision: 24 April 2020
Publication Date:
28 May 2020 (online)
![](https://www.thieme-connect.de/media/synlett/202015/lookinside/thumbnails/st-2020-a0209-a_10-1055_s-0040-1707125-1.jpg)
Dedicated to Prof. Julius Rebek Jr. on the occasion of his 75th birthday
Abstract
This Account describes our efforts over the last decade to synthesize self-assembled metal–ligand cage complexes that display reactive functional groups on their interiors. This journey has taken us down a variety of research avenues, including studying the mechanism of reversible self-assembly, analyzing ligand self-sorting properties, post-assembly reactivity, molecular recognition, and binding studies, and finally reactivity and catalysis. Each of these individual topics are discussed here, as are the lessons learned along the way and the future research outlook. These self-assembled hosts are the closest mimics of enzymes to date, as they are capable of size- and shape-selective molecular recognition, substrate activation and turnover, as well as showing less common ‘biomimetic’ properties such as the ability to employ cofactors in reactivity, and alter the prevailing mechanism of the catalyzed reactions.
1 Introduction
2 Paddlewheels and Self-Sorting Behavior
3 First-Row Transition-Metal-Mediated Assembly: Sorting and Stereochemical Control
4 Post-Assembly Reactivity
5 Molecular Recognition and Catalysis
6 Conclusions and Outlook
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