Photochemical conversion of sugar dimethylthiocarbamates into deoxy sugars.
Protected sugar derivatives having one free hydroxyl group may be deoxygenated at the alcoholic position by ultraviolet irradiation of the corresponding dimethylthiocarbamic esters; a concomitant process leads also to the original alcohol. Thus, on photolysis, the 6-dimethylthiocarbamate (1) of 1,2:3,4-di-O-isopropylidene-alpha-D-galactopyranose (3) gives 6-deoxy-1,2:3,4-di-O-isopropylidene-alpha-D-galactopyranose (2) together with 3. Likewise, the 4-dimethylthiocarbamate (6) of 1,6-anhydro-2,3-O-isopropylidene-beta-D-mannopyranose (8) gives a mixture of the 4-deoxy derivative 7 and the alcohol 8. 3-Deoxy-1,2:5,6-di-O-isopropylidene-alpha-D-ribo-hexofuranose (10) was obtained by irradiation of 3-O-(dimethylthiocarbamoyl)-1,2:5,6-di-O-isopropylidene-alpha-D-glucofuranose (9), and was accompanied by 1,2:5,6-di-O-isopropylidene-alpha-D-glucofuranose (11). The 3-deoxy-3-iodo analog (14) of 11 underwent conversion into 10 by photolysis, and the deoxy sugar 10 was also prepared from 3,3'-dithiobis(1,2:5,6-di-O-isopropylidene-alpha-D-glucofuranose) (12) by the action of Raney nickel. Photolysis of the 2-dimethylthiocarbamate (16) of methyl 3,4-O-isopropylidene-beta-L-arabinopyranoside (18 gave the 2-deoxy derivative (17), together with the parent alcohol 18, and the same pair of products was obtained by the action of tributylstannane on the 2-(methylthio)thiocarbonyl derivative (19) of 18, although the dimethylthiocarbamate 16 was unreactive toward tributylstannane.
D001089:Arabinose / Q000031:analogs & derivatives; D003837:Deoxy Sugars / Q000138:chemical synthesis*; D005690:Galactose / Q000031:analogs & derivatives; D005947:Glucose / Q000031:analogs & derivatives; D006601:Hexoses; D008358:Mannose / Q000031:analogs & derivatives; D000432:Methanol; D010777:Photochemistry; D013859:Thiocarbamates
D003837:Deoxy Sugars; D006601:Hexoses; D013859:Thiocarbamates; D001089:Arabinose; D005947:Glucose; D008358:Mannose; D005690:Galactose; D000432:Methanol