Carbohydrates intramolecular hydrogen bonds

Kurahashi, T. Mizutani, T. Yoshida, J., Effect of intramolecular hydrogen-bonding network on the relative reactivities of carbohydrate OH groups. J. Chem. Soc. Perkin Trans. 1 1999, 465-473. 

Vicente, V. Martin, J. Jimenez-Barbero, J. Chiara, J. L. Vicent, C., Hydrogenbonding cooperativity Using an intramolecular hydrogen bond to design a carbohydrate derivative with a cooperative hydrogen-bond donor centre. Chem. Eur. J. 2004,10, 4240-4251. 

In addition to the effect of polar groups (discussed above) and the electrostatic effect of neighboring anionic charge, there are other factors that affect carbohydrate acidity. Among them are steric and entropy effects and intramolecular hydrogen bonding. 

K. Bock and R. U. Lemieux, The conformational properties of sucrose in aqueous solution Intramolecular hydrogen-bonding, Carbohydr. Res., 100 (1982) 63-74. 

The Conformational Properties, including Intramolecular Hydrogen Bonding, of Maltose and Related Compounds. E. Alvarado, O. Hindsgaul, R. U. Lemieux, K. Bock, and H. Pedersen, Abstr. XHth Int. Carbohydr. Symp., July 1-7 (1984) Utrecht, The Netherlands, p. 480. 

M. L. de la Paz, G. Ellis, S. Penades, and C. Vincent, Conformational restriction by intramolecular hydrogen bonding. Carbohydrate-carbohydrate self-assembly, Tetrahedron Lett., 38 (1977) 1659-1662. 

J. M. Macleod, L. R. Schroeder, and P. A. Seib, Selective esterification of 1,6-anhydrohexopyranoses the possible role of intramolecular hydrogen-bonding, Carbohydr. Res., 30 (1973) 337-347. 

Table 9.2. Intramolecular hydrogen bonds between syndiaxially oriented O-H groups in carbohydrate crystal structures...

Jeffrey GA, Fasiska EY (1972) Conformation and intramolecular hydrogen-bonding in the crystal structure of potassium D-gluconate monohydrate. Carbohydr Res 21 187-199... 

Fig. 11. Interresidue linkages in carbohydrates chains (illustrated for some glucose dimers). Linkage conformation is defined by the dihedral angles 4>, ij/) or (4>, j/, o>). The intramolecular hydrogen bonds are also indicated.

In dimethyl sulfoxide, exchange of hydroxyl protons is slow enough that hydroxyl protons are observed separately coupled to adjacent CH protons in the NMR spectra of carbohydrates [237,238,239]. Hydroxyl protons involved in intramolecular hydrogen bonds are shielded in comparison to those involved in intermolecular hydrogen bonds to dimethyl sulfoxide [240,241]. The coupling constants can be used in conjunction with Karplus-type relationships [242,243] to identify the orientation of the OH groups. The J values observed for... 

M. M. Deshmukh, L. J. Bartolotti, and S. R. Gadre, Intramolecular hydrogen bonding and cooperative interactions in carbohydrates via the molecular tailoring approach, J. Phys. Chem. A, 112 (2008) 312-321. 

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