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.