title: DFT calculations of the anomeric and exo-anomeric effect of the hydroperoxy and peroxy groups.
abstract: DFT calculations were carried out on axially and equatorially oriented 2-hydroperoxy and 2-peroxy tetrahydropyran, cyclohexyl hydroperoxide, hydroperoxides of 2,3-unsaturated hexapyranoses, and hydroperoxides of OMe and OBn substituted derivatives of 2-deoxy-glucopyranose and 2-deoxy-galactopyranose to investigate the anomeric and exo-anomeric effects of these groups. The structure and energy of the conformers were calculated at the B3LYP/6-311++G** level. Calculations showed that the peroxy anion group exhibits a strong anomeric effect, comparable in magnitude to the methoxy group, and that the anomeric effect of the hydroperoxy group is similar to the hydroxyl group. These results revealed that hydroperoxy and peroxy anion groups display an exo-anomeric effect, but the orientation around the C1-O1 bond is also affected by hydrogen bonding and electrostatic interactions.
authors.affiliation: Institute of Organic Chemistry of the Polish Academy of Sciences, PL-01 224 Warsaw, Poland.
authors.forename: Wioletta
authors.initials: W
authors.lastname: Kośnik
authors.forename: Wojciech
authors.initials: W
authors.lastname: Bocian
authors.forename: Marek
authors.initials: M
authors.lastname: Chmielewski
authors.forename: Igor
authors.initials: I
authors.lastname: Tvaroska
mesh_terms: D000838:Anions / Q000737:chemistry*; D006860:Hydrogen Bonding; D006861:Hydrogen Peroxide / Q000737:chemistry*; D008968:Molecular Conformation; D015394:Molecular Structure; D010545:Peroxides / Q000737:chemistry*
chemical_list: D000838:Anions; D010545:Peroxides; D006861:Hydrogen Peroxide