Glycosidic bond formation in aqueous solution: on the oxocarbenium intermediate.
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.
Stubbs
John M
JM
Lehrstuhl für Theoretische Chemie, Ruhr-Universität Bochum, 44780 Bochum, Germany. stubbs@chem.umn.edu
Marx
Dominik
D
D006027:Glycosides / Q000737:chemistry*; D000432:Methanol / Q000737:chemistry; D008956:Models, Chemical; D008958:Models, Molecular; D011714:Pyrans / Q000737:chemistry; D012996:Solutions; D014867:Water / Q000737:chemistry
D006027:Glycosides; D011714:Pyrans; D012996:Solutions; D014867:Water; D000432:Methanol