title: Induced-fit catalysis of corannulene bowl-to-bowl inversion.
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.
authors.affiliation: Center for the Chemistry of Integrated Systems, Department of Chemistry, Northwestern University, 2145 Sheridan Road, Evanston, Illinois 60208, USA.
authors.forename: Michal
authors.initials: M
authors.lastname: Juríček
authors.affiliation: Center for the Chemistry of Integrated Systems, Department of Chemistry, Northwestern University, 2145 Sheridan Road, Evanston, Illinois 60208, USA.
authors.forename: Nathan L
authors.initials: NL
authors.lastname: Strutt
authors.affiliation: Center for the Chemistry of Integrated Systems, Department of Chemistry, Northwestern University, 2145 Sheridan Road, Evanston, Illinois 60208, USA.
authors.forename: Jonathan C
authors.initials: JC
authors.lastname: Barnes
authors.affiliation: Organic Chemistry Institute (OCI), University of Zürich, Winterthurerstrasse 190, Zürich, CH-8057, Switzerland.
authors.forename: Anna M
authors.initials: AM
authors.lastname: Butterfield
authors.affiliation: Center for the Chemistry of Integrated Systems, Department of Chemistry, Northwestern University, 2145 Sheridan Road, Evanston, Illinois 60208, USA.
authors.forename: Edward J
authors.initials: EJ
authors.lastname: Dale
authors.affiliation: 1] Organic Chemistry Institute (OCI), University of Zürich, Winterthurerstrasse 190, Zürich, CH-8057, Switzerland [2] School of Pharmaceutical Science and Technology, Tianjin University (A210/Building 24), 92 Weijin Road, Nankai District, Tianjin, 300072 PRC, China.
authors.forename: Kim K
authors.initials: KK
authors.lastname: Baldridge
authors.affiliation: Center for the Chemistry of Integrated Systems, Department of Chemistry, Northwestern University, 2145 Sheridan Road, Evanston, Illinois 60208, USA.
authors.forename: J Fraser
authors.initials: JF
authors.lastname: Stoddart
authors.affiliation: 1] Organic Chemistry Institute (OCI), University of Zürich, Winterthurerstrasse 190, Zürich, CH-8057, Switzerland [2] School of Pharmaceutical Science and Technology, Tianjin University (A210/Building 24), 92 Weijin Road, Nankai District, Tianjin, 300072 PRC, China.
authors.forename: Jay S
authors.initials: JS
authors.lastname: Siegel
mesh_terms: D002384:Catalysis; D009682:Magnetic Resonance Spectroscopy; D011084:Polycyclic Aromatic Hydrocarbons / Q000737:chemistry*; D013816:Thermodynamics
chemical_list: D011084:Polycyclic Aromatic Hydrocarbons; C434863:corannulene