Some aspects of stereochemistry and hydrogen bonding of carbohydrates related to polysaccharide conformations

Some general rules governing hydrogen bonding at the ring oxygens of furanosides, pyranosides, and bridge oxygens of glycosides have been formulated from existing data on crystal structures of carbohydrates. Ring oxygens of the majority of the glycopyranosides in the hemiacetal or acetal form are involved in hydrogen bonding such that the hydrogen bond direction is usually equatorial to the ring plane and not axial. In contrast, there are no known examples of ring oxygens of glycofuranosides and methyl‐glycopyranosides displaying hydrogen bonding in the crystal. Also, the bridge oxygens of glycosides are not involved in hydrogen bonding. The observed shortening in the exocyclic and endocyclic anomeric C(1)O bonds and the geminal CO bonds indicate that compounds with two oxygen atoms attached to the same saturated carbon atom may participate in double‐bond‐no‐bond resonance interaction in the same manner as difluoromethane. It is also possible that under these circumstances the carbon atom exhibits greater than tetracovalency. The “anomeric effect” may also be related to (a) the differences in the “double bonding” or bond shortening in the anomeric CO bonds of the anomeric glycopyranosides, (b) the shorter intramolecular O(1)…︁O(5) non‐bonded interaction, and (c) the smaller O(1)C(1)O(5) valence angle in the equatorial anomer compared to the axial anomer. An analysis has been made of the energetically preferred conformations about the glycosyl and glycosidic bonds of 1,4‐ and 1,3‐polysuc‐charides. In the 1a, 4e‐glycopyranosides the projected angle ϕ1 [O(5)C(1)OR, where R = C or H] is positive, while it is negative in the 1e, 4e‐glycopyranosides. Angle ϕ2 [C(1)OC(4′)C(3′)] is positive in both the 1,4‐anomeric polyglycosides. 1e, 4e‐ and 1a, 4e ‐polysaccharides are stabilized by intramolecular O(5)…︁HO(3′) and O(2′)…︁O(3′) hydrogen bonding, respectively, and generate linear and helical (cyclic) structures, respectively. 1e, 3e‐ and 1a, 3e‐polysaccharides may be stablized by one of two possible intramolecular hydrogen‐bonding schemes such that the 1a, 3e ‐polysaccharides generate helical structures while the 1a, 3e‐polysaccharides generate nonhelical structures. The conformation about the C(5)C(6) bond in the pyranosides falls into two groups where the angle ϕ00 [O(5)C(5)C(6)O(6)] is either positive, ∼+60 ± 30°, or negative, ∼–60 ± 30°, the former conformation being found more frequently. In the furanosides the latter conformation is preferred.

[1]  G. A. Jeffrey,et al.  The crystal structure of - D -glucurono-?-lactone , 1967 .

[2]  Katsumi Kimura,et al.  Structures of Dimethyl Ether and Methyl Alcohol , 1959 .

[3]  W. M. MacIntyre,et al.  The Crystal and Molecular Structure of 5-Fluoro-2′-Deoxy-β-Uridine , 1964 .

[4]  G. A. Jeffrey,et al.  The crystal structure of 5,5-dihydroxybarbituric acid trihydrate. , 1965, Acta crystallographica.

[5]  H. Bent.  Bond Shortening by Electronegative Substituents , 1960 .

[6]  G. Gurr.  The crystal structures of the dihydrated potassium and rubidium salts of β‐d‐glucuronic acid , 1963 .

[7]  H. A. Levy,et al.  α-D-Glucose: Precise Determination of Crystal and Molecular Structure by Neutron-Diffraction Analysis , 1965, Science.

[8]  A. Hordvik,et al.  Refinement of the Crystal Structure of beta-Arabinose. , 1961 .

[9]  J. Lindgren,et al.  The Structure of 2-Deoxy-ribose. , 1960 .

[10]  B. Sheldrick,et al.  The crystal structure of α‐methyl‐d‐galactoside 6‐bromohydrin , 1965 .

[11]  Kim Sh,et al.  The crystal structure of β-dl-arbinose , 1967 .

[12]  H. A. Levy,et al.  Sucrose: Precise Determination of Crystal and Molecular Structure by Neutron Diffraction , 1963, Science.

[13]  D. G. Watson,et al.  The crystal structure of deoxyadenosine monohydrate. , 1965, Acta crystallographica.

[14]  F. Jellinek,et al.  The structure of muscarine , 1957 .

[15]  D. Cruickshank.  Errors in bond lengths due to rotational oscillations of molecules , 1956 .

[16]  S. Furberg.  The crystal structure of cytidine , 1950 .

[17]  M. Sundaralingam,et al.  Stereochemistry of nucleic acid constituents , 1965 .

[18]  C. Romming,et al.  A refinement of the crystal structure of cytidine , 1965 .

[19]  M. Sundaralingam,et al.  Stereochemistry of nucleic acid constituents: II. A comparative study , 1965 .

[20]  M. Sundaralingam.  Stereochemistry of nucleic acid constituents. 3. Crystal and molecular structure of adenosine 3'-phosphate dihydrate (adenylic acid b). , 1966, Acta crystallographica.

[21]  P. Hermans,et al.  Über die Gestalt und die Beweglichkeit des Moleküls der Zellulose , 1943 .

[22]  L. Pauling.  The Nature Of The Chemical Bond , 1939 .

[23]  William N. Lipscomb,et al.  The crystal and molecular structure of cellobiose , 1961 .

[24]  M. Kabayama,et al.  THE THERMODYNAMICS OF MUTAROTATION OF SOME SUGARS: II. THEORETICAL CONSIDERATIONS , 1958 .

[25]  W. Cochran,et al.  The crystal structure of sucrose sodium bromide dihydrate , 1947, Proceedings of the Royal Society of London. Series A. Mathematical and Physical Sciences.

[26]  C. Beevers,et al.  The crystal structure of a-rhamnose monohydrate , 1957 .

[27]  F. Shafizadeh.  Formation and cleavage of the oxygen ring in sugars. , 1958, Advances in carbohydrate chemistry.

[28]  L. Brockway.  The Structures of the Fluorochloromethanes and the Effect of Bond Type on Chemical Reactivity , 1937 .

[29]  V. Schomaker,et al.  Some Revisions of the Covalent Radii and the Additivity Rule for the Lengths of Partially Ionic Single Covalent Bonds , 1941 .

[30]  G. A. Jeffrey,et al.  CRYSTAL-STRUCTURE ANALYSIS IN CARBOHYDRATE CHEMISTRY. , 1964, Advances in carbohydrate chemistry.

[31]  M. Sundaralingam,et al.  CONFORMATIONS OF THE FURANOSE RING IN NUCLEIC ACIDS AND OTHER CARBOHYDRATE DERIVATIVES IN THE SOLID STATE. , 1965, Journal of the American Chemical Society.

[32]  J.F.A. Williams.  Filling of antibonding orbitals—II , 1962 .

[33]  S. Kim,et al.  The crystal structure of a- L -sorbose , 1967 .

[34]  Y. Okaya.  The plant sulfolipid: a crystallographic study , 1964 .

[35]  C. Djerassi,et al.  The Crystal and Molecular Structure of beta-Lyxose. , 1966 .

[36]  D. Peters.  Problem of the Lengths and Strengths of Carbon—Fluorine Bonds , 1963 .

[37]  K. Trueblood,et al.  THE CRYSTAL AND MOLECULAR STRUCTURE OF D(+)-BARIUM URIDINE-5'-PHOSPHATE. , 1965, Acta crystallographica.

[38]  D. W. Jones.  Crystalline modifications of cellulose. Part V. A crystallographic study of ordered molecular arrangements , 1960 .

[39]  W. G. Ferrier.  The crystal and molecular structure of -D-glucose , 1963 .

[40]  A. Mathieson,et al.  The crystal and molecular structure of methyl‐1‐thio‐β‐d‐xylopyranoside , 1966 .