Regioselective resolution of 1,n-diols catalysed by lipases: a rational explanation of the enzymatic selectivity

The regioselective acylation of different phenylalkanediols catalysed by po rcine pancreatic lipase (PPL) was used for modelling the enzymatic substrat e recognition. Thus, different racemic or prochiral (1,n)-diols, with n ran ging from 2 to 6, were resolved via transesterification with vinyl acetate, and the results obtained (yield, reaction rate, enantioselectivity) were e xplained according to the microcrystalline enzyme structure. A logical mode l for explaining the enzyme regio-and stereoselectivity is proposed, based on literature data reporting similar recognition patterns for some other Li pases; our model is built on three residues of the active site (Ser153, Phe 216 and His264), which turned out to be crucial for the substrate binding a nd transformation. Furthermore, some other tentative models proposed for PP L recognition are explained with our criterion. (C) 2001 Elsevier Science B .V. All rights reserved.