Sugars Containing a Carbon-phosphorus Bond. I. Photochemical Addition of Diethyl Thiophosphonate to Unsaturated Sugars

Sugars containing a carbon-phosphorus bond were synthesized by the photochemical addition of diethyl thiophosphonate to unsaturated sugars. By UV illumination from a high-pressure mercury lamp in the presence of diethyl thiophosphonate, -D-glucal gave 1,5-anhydro-2-deoxy-2-(diethyl thiophosphonate)-D-glucit; 3-deoxy-1,2;5,6-di-O-isopropylidene-α-D-erythro-hex-3-enose gave 1,2;5,6-di-O-isopropylidene-3-deoxy-3-(diethyl thiophosphonate)-α-D-glucofuranose and 1,2;5,6-di-O-isopropylidene-3-deoxy-3-(diethyl thiophosphonate)-α-D-galactofuranose (4:1 mol ratio); 6-O-benzyl-5-deoxy-1,2-O-isopropylidene-α-D-xylo-hexofuran-5-enose gave 6-O-benzyl-5-deoxy-5-(diethyl thiophosphonate)-1,2-O-isopropylidene-α-D-glucofuranose and 6-O-benzyl-5-deoxy-5-(diethyl thiophosphonate)-1,2-O-isopropylidene-α-L-idofuranose (2:5 or 5:2 mol ratio), and 5-deoxy-l,2-O-isopropylidene-3-O-methyl-α-D-xylofuranose-4-ene gave 5-deoxy-5-(diethyl thiophosphonate)-1,2-O-isopropylidene-3-O-methyl-α-D-xylofuranose.