Abstract
The effect of high pressure (physical activation) and of water as medium (solvophobic interactions) is examined in Baylis-Hillman reactions. Whereas these reactions proceed usually slowly in aqueous solutions at ambient pressure, high pressure is revealed as a potent activation method to drive the reaction but only under neat conditions. In such way, various acrylic compounds react with aldehydes and even ketones, In addition, α, β-ethylenic compounds can undergo dimerization according to the Baylis-Hillman pathway. Multiactivation (pressure + solvophobic interactions) is of little value in these reactions, a result contrasting with those obtained in other organic reactions.