Dendroclefts: Optically active dendritic receptors for the selective recognition and chiroptical sensing of monosaccharide guests

TY - JOUR

T1 - Dendroclefts: Optically active dendritic receptors for the selective recognition and chiroptical sensing of monosaccharide guests

AU - Smith, D K

AU - Zingg, A

AU - Diederich, F

PY - 1999

Y1 - 1999

N2 - The enantiomerically pure dendritic receptors with cleft-type recognition sites (dendroclefts) of generation zero ((-)-G0), one ((-)-G1), and two ((-)-G2) (Fig. I) were prepared for the complexation of monosaccharides via H-bonding. They incorporate a rigid, optically active 9,9'-spirobi[9H-fluorene ] core bearing 2,6-bis(carbonylamino)pyridine moieties as H-bonding sites in the 2,2'-positions. The dendritic shells in (-)-G1 and (-)-G2 are made out of a novel type of dendritic wedges of the first (8; Scheme 2) and second (13; Scheme 3) generations, which contain only donor O-atoms and are attached to the H-bonding edges of the core via glycine spacers (Scheme 4). The formation of stable 1 :1 complexes (association constants K-a, between 100 and 600 M-1, T = 298 K; Table 2) between the three receptors and pyranosides in CHCl3, was confirmed by LH-NMR and CD binding titrations as well as by Job plot analyses. The degree of dendritic branching was found to exert a profound effect on the stereoselectivity of the recognition processes. The binding enantioselectivity decreases with increasing degree of branching, whereas the diastereoselectivity increases. The H-1-NMR analysis showed that the N-H...O H-bonds between the amide NH groups around the core and the sugar O-atoms become weakened with increasing dendritic generation, presumably due to steric factors and competition from intramolecular H-bonding between these amide groups and the O-atoms of the dendritic shell. The chiroptical properties of the dendroclefts respond to guest binding in a stereoselective manner. Whereas large differential changes are seen in the circular dichroism (CD) spectra of (-)-G0 and (-)-G1 upon complexation of the enantiomeric monosaccharides (Figs. 3 and 4), the CD spectra of the higher- generation derivative (-)-G2 respond to a lesser extent to guest complexation (Fig. 5). This is indicative of a different binding geometry, more remote from the core chromophore. With their higher masses, the dendroclefts (-)-G1 and (-)-G2 are readily recycled from host-guest solutions by gel-permeation chromatography. The strong CD sensory response and the easy recyclability suggest applications of chiral dendroclefts as sensors for biologically important molecules.

AB - The enantiomerically pure dendritic receptors with cleft-type recognition sites (dendroclefts) of generation zero ((-)-G0), one ((-)-G1), and two ((-)-G2) (Fig. I) were prepared for the complexation of monosaccharides via H-bonding. They incorporate a rigid, optically active 9,9'-spirobi[9H-fluorene ] core bearing 2,6-bis(carbonylamino)pyridine moieties as H-bonding sites in the 2,2'-positions. The dendritic shells in (-)-G1 and (-)-G2 are made out of a novel type of dendritic wedges of the first (8; Scheme 2) and second (13; Scheme 3) generations, which contain only donor O-atoms and are attached to the H-bonding edges of the core via glycine spacers (Scheme 4). The formation of stable 1 :1 complexes (association constants K-a, between 100 and 600 M-1, T = 298 K; Table 2) between the three receptors and pyranosides in CHCl3, was confirmed by LH-NMR and CD binding titrations as well as by Job plot analyses. The degree of dendritic branching was found to exert a profound effect on the stereoselectivity of the recognition processes. The binding enantioselectivity decreases with increasing degree of branching, whereas the diastereoselectivity increases. The H-1-NMR analysis showed that the N-H...O H-bonds between the amide NH groups around the core and the sugar O-atoms become weakened with increasing dendritic generation, presumably due to steric factors and competition from intramolecular H-bonding between these amide groups and the O-atoms of the dendritic shell. The chiroptical properties of the dendroclefts respond to guest binding in a stereoselective manner. Whereas large differential changes are seen in the circular dichroism (CD) spectra of (-)-G0 and (-)-G1 upon complexation of the enantiomeric monosaccharides (Figs. 3 and 4), the CD spectra of the higher- generation derivative (-)-G2 respond to a lesser extent to guest complexation (Fig. 5). This is indicative of a different binding geometry, more remote from the core chromophore. With their higher masses, the dendroclefts (-)-G1 and (-)-G2 are readily recycled from host-guest solutions by gel-permeation chromatography. The strong CD sensory response and the easy recyclability suggest applications of chiral dendroclefts as sensors for biologically important molecules.

KW - HYDROGEN-BONDING RECEPTORS

KW - MOLECULAR RECOGNITION

KW - CHIRAL DENDRIMERS

KW - ZINC PORPHYRINS

KW - BUILDING-BLOCKS

KW - BORONIC ACID

KW - WATER

KW - COMPLEXATION

KW - DENDROPHANES

KW - PYRANOSIDES

M3 - Article

SN - 0018-019X

VL - 82

SP - 1225

EP - 1241

JO - HELVETICA CHIMICA ACTA

JF - HELVETICA CHIMICA ACTA

IS - 8

ER -