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Deconvoluting the Role of Charge in a Supramolecular Catalyst

Journal Article · · Journal of the American Chemical Society
DOI:https://doi.org/10.1021/jacs.8b01701· OSTI ID:1464168
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  1. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Chemical Sciences Division; Univ. of California, Berkeley, CA (United States). Dept. of Chemistry
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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.

Research Organization:
Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Grant/Contract Number:
AC02-05CH11231
OSTI ID:
1464168
Journal Information:
Journal of the American Chemical Society, Journal Name: Journal of the American Chemical Society Journal Issue: 21 Vol. 140; ISSN 0002-7863
Publisher:
American Chemical Society (ACS)Copyright Statement
Country of Publication:
United States
Language:
English

References (40)

Supramolecular Catalysis of a Unimolecular Transformation: Aza-Cope Rearrangement within a Self-Assembled Host journal December 2004
Enzyme-like Control of Carbocation Deprotonation Regioselectivity in Supramolecular Catalysis of the Nazarov Cyclization journal September 2011
An Autocatalytic System of Photooxidation-Driven Substitution Reactions on a FeII4L6Cage Framework journal October 2015
Supramolecular Chemistry—Scope and Perspectives Molecules, Supermolecules, and Molecular Devices(Nobel Lecture) journal January 1988
The Taming of Cyclobutadiene journal August 1991
Enzyme Mechanisms, Models, and Mimics journal April 1996
Superamolecular Self-Recognition and Self-Assembly in Gallium(III) Catecholamide Triple Helices journal August 1997
Self-Assembled Molecular Capsules-Even More Than Nano-Sized Reaction Vessels journal February 2005
Functional Molecular Flasks: New Properties and Reactions within Discrete, Self-Assembled Hosts journal April 2009
Enzyme Mimics Based Upon Supramolecular Coordination Chemistry journal October 2010
Switchable Catalysis with a Light-Responsive Cavitand journal September 2011
Formation of a Highly Reactive Cobalt Nanocluster Crystal within a Highly Negatively Charged Porous Coordination Cage journal March 2018
Synthesis and Structural Characterization of Hexacoordinate Silicon, Germanium, and Titanium Complexes of theE. coliSiderophore Enterobactin journal July 2013
Origins of Large Rate Enhancements in the Nazarov Cyclization Catalyzed by Supramolecular Encapsulation journal February 2014
Effects of Ligands, Cluster Size, and Charge State in Gas-Phase Catalysis: A Happy Marriage of Experimental and Computational Studies journal September 2012
The Nazarov cyclization in organic synthesis. Recent advances journal August 2005
Recent advances in molecular recognition with tetrathiafulvalene-based receptors journal December 2016
Self-Assembled Nanoreactors journal March 2005
Electrostatic Basis for Enzyme Catalysis journal August 2006
Supramolecular Catalysis in Metal–Ligand Cluster Hosts journal April 2015
Structural Consequences of Anionic Host−Cationic Guest Interactions in a Supramolecular Assembly journal January 2009
Catalysis and chiral recognition through designed complexation of transition states in transacylations of amino ester salts journal February 1976
A Cleavage Reaction of α-Allylbenzylamines journal April 1950
Alkane Oxidation via Photochemical Excitation of a Self-Assembled Molecular Cage journal August 2004
The Big Squeeze:  Guest Exchange in an M 4 L 6 Supramolecular Host journal June 2005
Enzymelike Catalysis of the Nazarov Cyclization by Supramolecular Encapsulation journal May 2010
Selective Monoterpene-like Cyclization Reactions Achieved by Water Exclusion from Reactive Intermediates in a Supramolecular Catalyst journal October 2012
Empirical and Theoretical Insights into the Structural Features and Host–Guest Chemistry of M8L4 Tube Architectures journal February 2014
Aza Cope Rearrangement of Propargyl Enammonium Cations Catalyzed By a Self-Assembled “Nanozyme” journal August 2008
Cavity-Tailored, Self-Sorting Supramolecular Catalytic Boxes for Selective Oxidation journal December 2008
Electric-Field-Assisted Anion−π Catalysis journal May 2017
Electrostatic Origin of the Catalytic Effect of a Supramolecular Host Catalyst journal November 2012
Terpene cyclization catalysed inside a self-assembled cavity journal February 2015
Highly efficient catalysis of the Kemp elimination in the cavity of a cubic coordination cage journal February 2016
Reactivity within a confined self-assembled nanospace journal January 2008
Intramolecular hydroalkoxylation catalyzed inside a self-assembled cavity of an enzyme-like host structure journal January 2015
The effect of host structure on the selectivity and mechanism of supramolecular catalysis of Prins cyclizations journal January 2015
Molecular catalysis: enhanced rates of thiolysis with high structural and chiral recognition in complexes of a reactive macrocyclic receptor molecule journal January 1978
Diels-Alder in Aqueous Molecular Hosts: Unusual Regioselectivity and Efficient Catalysis journal April 2006
A supramolecular microenvironment strategy for transition metal catalysis journal December 2015

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Confinement Effects in Catalysis Using Well-Defined Materials and Cages journal December 2018

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