Abstract
Stereoelectronic complementarity between the active site of an enzyme and the transition state of a reaction is one of the tenets of enzyme catalysis. This report illustrates the principles of enzyme catalysis (first proposed by Pauling and Jencks) through a well-defined model system that has been fully characterized crystallographically, computationally and kinetically. Catalysis of the bowl-to-bowl inversion processes that pertain to corannulene is achieved by combining ground-state destabilization and transition-state stabilization within the cavity of an extended tetracationic cyclophane. This synthetic receptor fulfils a role reminiscent of a catalytic antibody by stabilizing the planar transition state for the bowl-to-bowl inversion of (ethyl)corannulene (which accelerates this process by a factor of ten at room temperature) by an induced-fit mechanism first formulated by Koshland.
Original language | English (US) |
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Pages (from-to) | 222-228 |
Number of pages | 7 |
Journal | Nature chemistry |
Volume | 6 |
Issue number | 3 |
DOIs | |
State | Published - Mar 2014 |
ASJC Scopus subject areas
- Chemistry(all)
- Chemical Engineering(all)
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CCDC 950390: Experimental Crystal Structure Determination
Juríček, M. (Creator), Strutt, N. L. (Creator), Barnes, J. C. (Creator), Butterfield, A. M. (Creator), Dale, E. J. (Creator), Baldridge, K. K. (Creator), Stoddart, J. F. (Creator) & Siegel, J. S. (Creator), Cambridge Crystallographic Data Centre, 2014
DOI: 10.5517/cc10wyrl, http://www.ccdc.cam.ac.uk/services/structure_request?id=doi:10.5517/cc10wyrl&sid=DataCite
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