A Solvation-Assisted Model for Estimating Anomeric Reactivity. Predicted versus Observed Trends in Hydrolysis of n-Pentenyl Glycosides1
Citations Over TimeTop 14% of 1996 papers
Abstract
An attempt has been made to predict qualitative trends in reactivity at the anomeric center, using N-bromosuccinimide-induced hydrolysis of n-pentenyl glycosides (NPGs) as the experimental model. Calculated relative activation energies based on internal energy differences between a reactant and the associated intermediate are not always in agreement with experimental observations. However, solvation energies obtained by the generalized Born surface area model in MacroModel developed by Still et al. give modified activation energies that are in excellent agreement with the experimentally observed trends. It is shown that the solvation model does not disturb the normally observed reactivity trends that can be rationalized on the basis of internal energies alone. The value of the methodology has been demonstrated for several substrates by first calculating their relative activation energies, then testing them experimentally, and finding excellent agreement with predictions.
Related Papers
- → New solvation free energy function comprising intermolecular solvation and intramolecular self-solvation terms(2013)38 cited
- → Trityl Salt Catalyzed Stereoselective Glycosylation of Alcohols with 1-Hydroxyribofuranose(1996)36 cited
- → Extended solvent-contact model for protein solvation: Test cases for dipeptides(2013)5 cited
- → Stereoselective synthesis of (±)-ancistrofuran: stereoselective reduction of a γ-hydroxyketone(1984)14 cited
- SOLVATION FREE ENERY OF THIENO [3, 2 - b] PYRIMIDINE ANALOGS COMPRISING INTERMOLECULAR SOLVATION AND INTRAMOLECULAR SELF-SOLVATION(2014)