E. L. Albano, D. Horton
Dec 1, 1969
Citations
0
Influential Citations
29
Citations
Journal
Carbohydrate Research
Abstract
Abstract Oxidation of methyl 2,3,6-trideoxy-α- D - erythro -hexopyranoside (methyl α-amicetoside, 1 ) gave the 4-ketone 2 , which was converted into the oxime 3 and ( p -nitrophenyl)hydrazone. Hydrogenation of 3 in ethanolic hydrochloric acid over platinum gave a 2:3 mixture of methyl 4-amino-2,3,4,6-tetradeoxy-α- d - erythro -hexopyranoside hydrochloride and the D - threo isomer which, on N -dimethylation gave methyl 2,3,4,6-tetradeoxy-4-(dimethylamino)-α- D - erythro -hexopyranoside ( 8 ) and the D - threo isomer ( 11 ). Hydrolysis of 8 gave crystalline 2,3,4,6-tetradeoxy-4-(dimethylamino)- D - erythro -hexose (forosamine), and hydrolysis of 11 gave 2,3,4,6-tetradeoxy-4-(dimethylamino)- D - threo -hexose. Reduction of the ketone 2 with lithium aluminum hydride regenerated the starting alcohol 1 stereospecifically. Base-catalyzed deuterium-exchange converted ketone 2 into its 3,3-dideuterio derivative. Treatment of 2 with base, and subsequently with ( p -nitrophenyl)hydrazine, in the presence of deuterium oxide, gave a 3,3,5-trideuterio ( p -nitrophenyl)hydrazone derivative.