Deconvoluting the Role of Charge in a Supramolecular Catalyst

Hong, Cynthia M.; Morimoto, Mariko; Kapustin, Eugene A.; Alzakhem, Nicola; Bergman, Robert G.; Raymond, Kenneth N.; Toste, F. Dean

doi:10.1021/jacs.8b01701

Title: Deconvoluting the Role of Charge in a Supramolecular Catalyst

Journal Article · Wed May 16 00:00:00 EDT 2018 · Journal of the American Chemical Society

DOI:https://doi.org/10.1021/jacs.8b01701· OSTI ID:1464168

^[1]; Morimoto, Mariko ^[1];

^[1]; Alzakhem, Nicola ^[1]; Bergman, Robert G. ^[1]; Raymond, Kenneth N. ^[1];

^[1]

Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Chemical Sciences Division; Univ. of California, Berkeley, CA (United States). Dept. of Chemistry

In this paper, 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. Finally, 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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Research Organization:: Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: AC02-05CH11231

OSTI ID:: 1464168

Journal Information:: Journal of the American Chemical Society, Vol. 140, Issue 21; ISSN 0002-7863

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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