Fluoro-substitution effects in deoxyfluoro-D-glucose derivatives: random conformational search and quantum chemical calculation.
The effect of substitution by the fluorine atom at different positions of D-glucose was investigated by quantum chemical calculation of the low-energy conformers. These were obtained through the Random conformational search method. The geometries of conformers were optimized at the RHF/6-31(d) level, then reoptimization and vibrational analysis were performed at the B3LYP/6-31+G(d) level. Single-point energies were calculated at the B3LYP/6-311++G(2d,2p) level. The free energies of solvation in water were calculated utilizing the AM1-SM5.4 solvation model. For all substitution positions, the ring conformation does not change much, and the pyranoid 4C1 conformers are dominant, while variations in the substitution site result in different effects in the network of hydrogen bonds, anomeric effect, the solvation free energy, and the ratio of alpha- and beta-anomers.
Zhou
Jin-Ming
JM
Department of Computer Chemistry and Cheminformatics, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 354 Fenglin Lu, 200032 Shanghai, China. zhoujm@mail.sioc.ac.cn
Zhou
Jun-Hong
JH
Zhang
Hua-Bei
HB
Dong
Xi-Cheng
XC
Chen
Min-Bo
MB
D003198:Computer Simulation; D003847:Deoxyglucose / Q000737:chemistry*; D005461:Fluorine / Q000737:chemistry*; D005947:Glucose / Q000737:chemistry*; D006845:Hydrocarbons, Fluorinated; D006860:Hydrogen Bonding; D008956:Models, Chemical; D008958:Models, Molecular; D008968:Molecular Conformation; D055672:Static Electricity; D013237:Stereoisomerism; D013816:Thermodynamics
D006845:Hydrocarbons, Fluorinated; D005461:Fluorine; D003847:Deoxyglucose; D005947:Glucose