Conformations and structure studies of sugar lactones. Part III. The composition and conformation of D-mannurono-gamma-lactone in solution, and the structural analysis of its beta anomer in the solid state.
Complete analyses of the proton and carbon chemical-shift assignments of D-mannurono-gamma-lactone (1) have been achieved by 1D and 2D NMR spectral measurements. At equilibrium, the anomeric alpha and beta forms were present in the ratio of 34:66 in D2O and 72:28 in Me2SO-d6. The solution data indicated that the dienvelope conformation 2E:E4 to be the favored conformation of 1 in solution. The crystal structure of 1 was determined, and it showed that the crystalline form is the beta anomer, a bicyclic structure, consisting of fused five-membered furanose and lactone rings, in agreement with an earlier deduction from chemical evidence. In contrast to the solution conformation, the furanose ring adopts a twist conformation lying between the 2(1)T and 1E conformations with phase angle (P) and pseudorotation amplitude (tau m) of -44.23 degrees and 37.9 degrees, respectively, whereas the lactone ring adopts an envelope E5 conformation slightly distorted towards 6T5 with a phase angle (P) of -22.3 degrees and a pseudorotation amplitude (tau m) of 18.4 degrees. The molecules are linked in the crystal through a hydrogen-bonding network that involves all hydroxyl groups as well as the ring oxygen atoms.
Department of Biochemistry, Louisiana State University, Baton Rouge 70803.
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Shalaby
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Fronczek
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Younathan
D002236:Carbohydrate Conformation; D006860:Hydrogen Bonding; D007783:Lactones / Q000737:chemistry*; D009682:Magnetic Resonance Spectroscopy; D008958:Models, Molecular; D012996:Solutions; D013237:Stereoisomerism
D007783:Lactones; D012996:Solutions; C091840:mannurono-gamma-lactone