SYNTHESIS OF ANTIMETABOLITES OF SUCROSE

The C-disaccharides lyxo-7,11-anhydro-6-deoxydodec-5-ulofuranose-(5,2) 7a and benzyloxysuccinyl-6-deoxydodec-5-ulofuranose-(5.2) 7b. antimet abolites of sucrose. the second of which is provided with a succinyl g roup which allows its linkage to biopolymers. have been synthesized. H ydroxymercuriation of the easily available 3-(2',3',4',6' tetra-O-benz yl-alpha-D-glucopyranosyl)prop-1-ene 1; followed by iodode-mercuriatio n. oxidation, and treatment of the so obtained iodo ketone with triphe nylphosphine afforded the stabilized ylide copyranosyl)-2-oxopropylide ne-triphenylphosphorane 2. Reaction of the ylide 2 with a properly pro tected D-glyceraldehyde 3 afforded the alpha,beta-unsaturated ketone 4 with a 12-carbon-atom skeleton, the stereoselective osmylation of whi ch, followed by deprotection. gave the C-disaccharide 7a. To obtain th e succinylated C-disaccharide 7b, )-2-O-benzyl-3-O-(benzyloxysuccinyl) glyceraldehyde 3b was employed, which was obtained by enzymic benzylox ysuccinylation of 2-O-benzylglycerol and subsequent oxidation.