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Conformational analysis of trehalose disaccharides and analogues using MM3
Author(s) -
Dowd Michael K.,
Reilly Peter J.,
French Alfred D.
Publication year - 1992
Publication title -
journal of computational chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.907
H-Index - 188
eISSN - 1096-987X
pISSN - 0192-8651
DOI - 10.1002/jcc.540130113
Subject(s) - trehalose , glycosidic bond , chemistry , disaccharide , crystallography , molecule , anomer , stereochemistry , specific rotation , computational chemistry , organic chemistry , enzyme
Energy surfaces for the relative orientations of the pyranosyl rings of α,α‐, α,β‐, and β,β‐trehalose and analogues were generated with MM3. Sixteen starting conformations of the rotatable side groups of α,β‐trehalose were considered, while only 10 conformations were needed for α,α‐ and β,β‐trehalose because of molecular symmetry. Energies were calculated at 20° increments of the two torsional angles of the glycosidic linkage, but otherwise the molecules were fully relaxed. The structure at the overall minimum for α,α‐trehalose agrees well with that found in crystal structures, and also agrees with interpretations of NMR and optical rotation data. The energy surfaces for the three trehaloses differ greatly from each other, but are each similar to those for the corresponding three 2‐(6‐methyltetrahydropyran‐2‐yloxy)6‐methyltetrahydropyrans. This suggests that linkage type (axial or equatorial) is more important than exocyclic substituents in determining trehalose conformations. A comparison with surfaces from the corresponding 5a‐carba trehalose analogues illustrates that the exo‐anomeric effect is important in determining disaccharide conformation.