Computational insight into the reaction intermediates in the glycosylation reaction assisted by donor heteroatoms.
We studied the geometric and electronic structure of several cations (9 and 18-23) that are usually proposed as intermediates for glycosylation reactions using DFT methods. For ions 9 and 18-23 the geometries obtained corresponded to an open ion (6b type) irrespective of the exocyclic heteroatom (S, Se, I) and the size of the cycle (furanoses as well as pyranoses). We studied how substituents bonded to the exocyclic heteroatom (R in SR and SeR) affect the structure of ions and found that the geometry approached that of episulfonium and episelenonium ions (6a type) when the substituents were electron donors. The tert-butyl group and the 2,4,6-trimethyl- and 2,4,6-trimethoxyphenyl and trimethylsilyl groups produced the strongest of these effects. The presence of an electron-withdrawing group (CO-CF(3)) bonded to the hydroxymethyl group produced a similar but weaker effect. We analyzed this behavior in terms of molecular orbital interactions.
Bravo
Fernando
F
Departament de Química Analítica i Química Orgànica, Universitat Rovira i Virgili, Imperial Tàrraco 1, 43005 Tarragona, Spain.
Viso
Antonio
A
Alcázar
Eva
E
Molas
Pineda
P
Bo
Carles
C
Castillón
Sergio
S
D002412:Cations / Q000737:chemistry; D003500:Cyclization; D005663:Furans / Q000737:chemistry; D006031:Glycosylation; D008958:Models, Molecular; D015394:Molecular Structure; D009005:Monosaccharides / Q000737:chemistry*; D010084:Oxidation-Reduction; D011714:Pyrans / Q000737:chemistry
D002412:Cations; D005663:Furans; D009005:Monosaccharides; D011714:Pyrans