A Theoretical Study of the Mechanism of the Desymmetrization of Cyclic meso-Anhydrides by Chiral Amino Alcohols.

ABSTRACT: The alcoholysis of cyclic meso-anhydrides catalyzed by β-amino alcohols has been investigated with DFT quantum mechanics to determine the mechanism of this reaction. Both nucleophilic catalysis and general base catalysis pathways are explored for methanol-induced ring opening of an anhydride catalyzed by a chiral amino alcohol. The nucleophilic pathway involves a late transition state with a high energy barrier. In this mechanism, methanolysis is expected to take place following the amine-induced ring opening of the anhydride. In the base-catalyzed mechanism, methanol attack on one carbonyl group of the meso-anhydride is assisted by the β-amino alcohol; the amine functionality abstracts the methanol proton. The chiral amino alcohol also catalyzes the reaction by stabilizing the oxyanion th

SUBMITTER: Dedeoglu B 

PROVIDER: S-EPMC3285420 | biostudies-literature | 2010 Sep

REPOSITORIES: biostudies-literature