Acylase I in the alcoholysis of alpha-substituted dicarboxylic acid estersand derivatives: enantio- and regioselectivity

Enantio- and regioselective butanolyses of alpha -substituted dimethyl succ inates (substituents: Me-, MeO2CCH2-, NH2-, AcHN-, PrCOHN-, HO-, MeO-, PrO- , AcO-, PrCO2-, HepCO(2)-, Cl- and Br-) and glutarates (substituents: PrCON H- and CbzNH-) and that of methyl pyroglutamate with acylase I enzymes have been studied. Acylase I-catalyzed reactions were totally regioselective pr oceeding exclusively at the sterically more hindered methyl ester group a t o the substituent. High enantioselectivities (E from 50 to much greater tha n 100) were observed only for the substrates containing CONH functionality in the substituent although the C-N bond was unreactive. The nature of the substituent influenced which of the two enantiomers reacted faster. (C) 200 0 Elsevier Science Ltd. All rights reserved.