1994 R.U. Lemieux Award Lecture Hydrolysis of acetals and ketals. Position of transition states along the reaction coordinates, and stereoelectronic effects

Abstract

Past and recent experimental results on the formation or hydrolysis (or isomerization) of various acetals and ketals including α-and β-glycoside models are presented. Ab initio investigations of simple acetals are also briefly reviewed as well as recent experimental and theoretical support evidence for a synperiplanar effect. A detailed study using the semi-empirical Hamiltonian AM1 defining the reaction pathway in the hydrolysis of various acetals and ketals is reported. This overall study shows that the hydrolysis of acetals and ketals is controlled by powerful stereoelectronic effects.