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Stereocontrolled synthesis of 6' deoxy 6' fluoro derivatives of methyl alpha sophoroside methyl alpha laminaribioside methyl alpha kojibioside and methyl alpha nigeroside



Stereocontrolled synthesis of 6' deoxy 6' fluoro derivatives of methyl alpha sophoroside methyl alpha laminaribioside methyl alpha kojibioside and methyl alpha nigeroside



Journal of Carbohydrate Chemistry 7(2): 317-336



Sequential tritylation, benzolation and detritylation of D-glucose, followed by resolution of the crude product by chromatography gave crystalline 1,2,3,4-tetra-O-benzoyl-.alpha.- (1) and .beta.-D-glucopyranose (2). Compound 1, 2, and the corresponding methyl .alpha.-glycoside 5 were treated with dimethylaminosulfur trifluoride (methyl DAST) to give, respectively, the 6-deoxy-6-fluoro derivatives 3, 4, and 6. Crystalline 2,3,4-tri-O-benzoyl-6-deoxy-6-fluoro-.alpha.-D-glucopyranosyl chloride (10) could be obtained from either 3, 4, or 6 by reaction with dichloromethyl methyl ether in the presence of anhydrous zinc chloride. Silver trifluoromethanesulfonate-promoted reaction of 10 with methyl 2-O-(9) and 3-O-benzyl-4,6-O-benzylidene-.alpha.-D-glucopyranoside (8) gave the corresponding, .beta.-linked disaccharides in high yield. Subsequent deprotection afforded the 6'-deoxy-6'-fluoro derivatives of methyl .alpha.-sophoroside (13) and methyl 6'-deoxy-6'-fluoro-.alpha.-laminaribioside (16). Condensation of 8 and 9 with 6-O-acetyl-2,3,4-tri-O-benzyl-.alpha.-D-glucopyranosyl chloride in the presence of silver perchlorate was highly stereoselective and produced the .alpha.-linked disaccharides 17 and 21, respectively, in excellent yield. Deacetylation of 17 and 21, followed by fluorination of the resulting alcohols 18 and 22 with methyl DAST and subsequent hydrogenolysis, gave 6'-deoxy-6'-fluoro derivatives of methyl .alpha.-kojibioside and methyl .alpha.-nigeroside 20 and 24, respectively.

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