Biologically relevant phosphoranes: structural characterization of glucofuranose- and xylofuranose-based phosphoranes.
Carbohydrate-based phosphoranes were synthesized by reacting 2,2'-ethylidenebis(4,6-di-tert-butylphenyl)fluorophosphite with 1,2-O-isopropylidene-alpha-D-glucofuranose, beta-chloralose, and 1,2-isopropylidene-alpha-D-xylofuranose to form the monocyclic biophosphoranes 1-3, respectively, in the presence of N-chlorodiisopropylamine. Synthesis of the monocyclic biophosphorane 4 was achieved by reacting tris(2,6-di-isopropylphenyl)phosphite with 1,2-O-isopropylidene-alpha-D-glucofuranose in the presence of N-chlorodiisopropylamine. X-ray analysis of 1-4 revealed trigonal bipyramidal structures with the carbohydrate components occupying axial-equatorial sites. An eight-membered ring in 1-3 occupied diequatorial sites of the trigonal bipyramid. Solution and solid state 31P and solution 19F, 1H, and 13C NMR measurements including variable temperature and correlation spectroscopy studies established retention of the solid state structure in solution. A dynamic equilibrium exists among two isomeric forms. These biophosphoranes serve as models for active sites of phosphoryl transfer enzymes. The rapid exchange process reorients the carbohydrate component of the trigonal bipyramidal phosphorane. At an active site, this type of pseudorotational behavior provides a mechanism that could bring another active site residue into play and account for a means by which some phosphoryl transfer enzymes express promiscuous behavior.
Department of Chemistry, University of Massachusetts, Amherst, Massachusetts 01003-9336, USA.
Natalya V
NV
Timosheva
A
A
Chandrasekaran
Robert R
RR
Holmes
D002698:Chloralose / Q000737:chemistry; D018360:Crystallography, X-Ray; D006860:Hydrogen Bonding; D009682:Magnetic Resonance Spectroscopy / Q000379:methods; D008958:Models, Molecular; D008968:Molecular Conformation; D009005:Monosaccharides / Q000737:chemistry*; D010753:Phosphoranes / Q000138:chemical synthesis / Q000737:chemistry*; D012680:Sensitivity and Specificity; D013237:Stereoisomerism
C516585:1,2-O-isopropylidene-alpha-D-glucofuranose; C516586:1,2-isopropylidene-alpha-D-xylofuranose; D009005:Monosaccharides; D010753:Phosphoranes; D002698:Chloralose