entropy effect

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The acceleration of a reaction that occurs when reactive groups are constrained in a productive orientation, either intermolecularly as on an enzyme surface, or intramolecularly as in a model compound. This phenomenon has been referred to variously as antichimaeric assistance, approximation, catalytic configuration, the Circe effect, coupling between conformational fluctuations, directed proton transfer, electric field effect, electrostatic stabilization, FARCE (freezing at the reactive centres of enzymes), gas-phase analogy, group transfer hydration, orbital perturbation theory, orbital steering, propinquity effect, proximity effect, rotamer distribution, stereoelectronic control; stereopopulation control, substrate anchoring, togetherness, torsional stress and vibrational activation. Page, M.I. and Jencks, W.P. (1987) Gazz. Chim. Ital. 117, 455-460

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