Glycosidic bond formation in aqueous solution: on the oxocarbenium intermediate

J Am Chem Soc. 2003 Sep 10;125(36):10960-2. doi: 10.1021/ja035600n.

Abstract

The mechanism of specific acid-catalyzed glycosidic bond formation between methanol and alpha-d-glucopyranoside in aqueous solution at 300 K was studied using Car-Parrinello molecular dynamics. The reaction was found to proceed through a non-solvent equilibrated oxocarbenium cation intermediate characterized by the loss of a hydrogen-bonding interaction between the ring oxygen and solvating water. The mechanism, which was found to be D(N)A(N) in nature, is discussed in detail.

Publication types

  • Research Support, Non-U.S. Gov't
  • Research Support, U.S. Gov't, Non-P.H.S.

MeSH terms

  • Glycosides / chemistry*
  • Methanol / chemistry
  • Models, Chemical
  • Models, Molecular
  • Pyrans / chemistry
  • Solutions
  • Water / chemistry

Substances

  • Glycosides
  • Pyrans
  • Solutions
  • Water
  • Methanol