An investigation of the pyranose ring interconversion path of α-l-idose calculated using density functional theory

Abstract The interconversion pathways of the pyranose ring conformation of α- l -idose from a 4 C 1 chair to other conformations were investigated using density functional calculations. From these calculations, four different ring interconversion paths and their transition state structures from the 4 C 1 chair to other conformations, such as B 3,O , and 1 S 3 , were obtained. These four transition-state conformations cover four possible combinations of the network patterns of the hydroxyl group hydrogen bonds (clockwise and counterclockwise) and the conformations of the primary alcohol group ( tg and gg ). The optimized conformations, transition states, and their intrinsic reaction coordinates (IRC) were all calculated at the B3LYP/6-31G ∗∗ level. The energy differences among the structures obtained were evaluated at the B3LYP/6-311++G ∗∗ level. The optimized conformations indicate that the conformers of 4 C 1 , 2 S O , and B 3,O have similar energies, while 1 S 3 has a higher energy than the others. The comparison of the four transition states and their ring interconversion paths, which were confirmed using the IRC calculation, suggests that the most plausible ring interconversion of the α- l -idopyranose ring occurs between 4 C 1 and B 3,O through the E 3 envelope, which involves a 5.21 kcal/mol energy barrier.