Molecular Recognition of Cyclitols by Neutral Polyaza-Hydrogen-Bonding Receptors: The Strength and Influence of Intramolecular Hydrogen Bonds between Vicinal Alcohols

Cooperative effects in two-dimensional ring-like networks of three-center hydrogen bonding interactions

“…These three-centered hydrogen bonds occur frequently in solid-state structures [1][2][3][4][5] and also in biologically relevant molecules. [6][7][8][9] An array of interlinked three-center hydrogen bonds is expected to exhibit cooperative enhancement just as it is observed in regular two-center hydrogen-bond arrays.…”

Molecular Recognition of Pyranosides by a Family of Trimeric, 1,1′-Binaphthalene-Derived Cyclophane Receptors

“…This is, at least in part, due to the complex three-dimensional structure of sugars which contain both hydrophilic and hydrophobic domains. Complexation by H-bonding in noncompetitive organic solvent environments is hampered by the fact that some of the strong intramolecular Hbonds within the sugar substrates themselves need to be disrupted [13] (for evaluations of intramolecular H-bonding strengths in sugars, see [14]). Recognition in H 2 O requires tight encapsulation of the limited hydrophobic surfaces of the sugars, yet an unfavorable desolvation of their H-bonding sites must be avoided.…”

“…The majority of the synthetic carbohydrate receptors form complexes in apolar solvents, for example in CCl 4 or CHCl 3 , taking advantage of H-bonding interactions as the major driving force for association [13] [15 ± 26]. In a few cases, optically active receptors were shown to bind octyl glucosides enantioselectively, with differences in stability between diastereoisomeric complexes D( DG 0 ) ranging between 0.4 [22a,b] and 0.8 kcal mol…”

Self‐Assembled Receptors that Stereoselectively Recognize a Saccharide

“…This trend in the complexation can be rationalized by the strength of the intramolecular hydrogen bonds in the pyranosides. [6][7][8] Complexation experiments using chiral assemblies (M)-4 3 ·(DEB) 12 were performed to further probe the stereoselectivity of the recognition of saccharide by the tetrarosette assemblies. In this case, instead of the racemic mixture of receptors (P)-1 3 ·(DEB) 12 and (M)-1 3 ·(DEB) 12 , the diastereomeric assembly (M)-4 3 ·(DEB) 12 was used as a complexing molecule.…”