Deconvoluting the Role of Charge in a Supramolecular Catalyst

Journal of the American Chemical Society
Cynthia M HongF Dean Toste

Abstract

We have demonstrated that the microenvironment of a highly anionic supramolecular catalyst can mimic the active sites of enzymes and impart rate accelerations of a million-fold or more. However, these microenvironments can be challenging to study, especially in the context of understanding which specific features of the catalyst are responsible for its high performance. We report here the development of an experimental mechanistic probe consisting of two isostructural catalysts. When examined in parallel transformations, the behavior of these catalysts provides insight relevant to the importance of anionic host charge on reactivity. These two catalysts exhibit similar host-substrate interactions, but feature a significant difference in overall anionic charge (12- and 8-). Within these systems, we compare the effect of constrictive binding in a net neutral aza-Cope rearrangement. We then demonstrate how the magnitude of anionic host charge has an exceptional influence on the reaction rates for a Nazarov cyclization, evidenced by an impressive 680-fold change in reaction rate as a consequence of a 33% reduction in catalyst charge.

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Citations

Jun 26, 2018·Angewandte Chemie·Lauren L K TaylorMaarten M J Smulders
Jul 25, 2019·Chemical Society Reviews·Yu FangHong-Cai Zhou
Jan 10, 2019·Frontiers in Chemistry·Valentinos MouarrawisJoost N H Reek
Dec 16, 2020·Proceedings of the National Academy of Sciences of the United States of America·Federico SebastianiMartina Havenith
Jan 21, 2021·Chemical Reviews·Luis Escobar, Pablo Ballester
May 20, 2021·Chemical Society Reviews·Giorgio OlivoStefano Di Stefano
Jul 3, 2021·Molecules : a Journal of Synthetic Chemistry and Natural Product Chemistry·Eugenia P KramarovaAlexander A Korlyukov
Apr 10, 2020·Journal of the American Chemical Society·Xiaoyang CaiBruce C Gibb
Nov 3, 2020·Journal of the American Chemical Society·Hiroyuki MiyamuraF Dean Toste
Dec 6, 2019·Journal of the American Chemical Society·Kenichi EndoMitsuhiko Shionoya
Apr 11, 2020·Journal of the American Chemical Society·Die LiuPingshan Wang
Dec 7, 2018·Chemical Reviews·Shinji Yamada
Oct 3, 2018·Accounts of Chemical Research·Cynthia M HongF Dean Toste
Jun 26, 2018·The Journal of Physical Chemistry Letters·Valerie Vaissier Welborn, Teresa Head-Gordon
Nov 26, 2020·Chemical Reviews·Edmundo G PercásteguiJonathan R Nitschke
Jan 8, 2020·Journal of the American Chemical Society·Stephen M BierschenkF Dean Toste
Aug 8, 2019·Journal of the American Chemical Society·Gantulga NorjmaaGregori Ujaque
Oct 2, 2021·Journal of the American Chemical Society·Iram F MansoorMark C Lipke
Oct 5, 2021·Chemistry, an Asian Journal·Bo Zhang, Joost N H Reek

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