High-pressure mechanistic delineation based on activation volumes

High-pressure kinetics is a useful tool for the determination and the assessment of mechanisms in organic chemistry. The volume of activation DeltaV* deduced from these kinetic measurements is an indicator of the position of the transition state. In addition, if accurately determined, DeltaV* permits the detection of fine mechanistic effects such as alteration of mechanism according to substrates within the same reaction type, operation of secondary orbital interactions in Diels-Alder cycloadditions, angular hydrogen transfer in ene reactions, etc. Copyright (C) 2001 John Wiley Sons, Ltd.