A model of proline as a “kinetic conglomerate” can rationalize both the nonlinear effect in proline-catalyzed aldol reactions observed in early studies and the linearity observed more recently, in a manner that remains compatible with the currently accepted one-proline reaction mechanism. Care must be taken to distinguish between equilibrium and kinetic effects in heterogeneous systems—and to separate these physical influences from nonlinear effects of a true chemical origin.
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Klußmann et al. (2006) studied this question.
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