P. Durette, E. P. Meitzner
Mar 2, 1981
Citations
0
Influential Citations
4
Citations
Journal
Carbohydrate research
Abstract
2-Methyl-[2-acetamido-4-O-acetyl-6-O-benzyl-3-O-(2-butenyl)-1,2-dideoxy-alpha-D-glucopyrano]-[2,1-d]-2-oxazoline (2), a glycosylating agent in which the three hydroxyl groups are blocked with protecting groups of differing "persistence", is of utility in the synthesis of oligosaccharides containing highly branched 2-acetamido-2-deoxy-D-glucosyl residues, and it was synthesized in a ten-step sequence from 2-acetamido-2-deoxy-D-glucose via allyl 2-acetamido-4,6-O-benzylidene-2-deoxy-beta-D-glucopyranoside (3). Alkylation of 3 with 2-butenyl (crotyl) bromide, hydrolysis of the benzylidene acetal group, benzylation of the 6-hydroxyl group, and acetylation of the 4-hydroxyl group afforded allyl 2-acetamido-4-O-acetyl-6-O-benzyl-3-O-(2-butenyl)-2-deoxy-beta-D-glucopyranoside(10). Treatment of 10 with chlorotris(tri-phenylphosphine)rhodium(I) gave mainly the corresponding 1-propenyl beta-glycoside, which was converted into oxazoline 2 by the action of mercuric chloride-mercuric oxide in acetonitrile. Glycosylation of benzyl 2-acetamido-3,6-di-O-benzyl-2-deoxy-alpha-D-glucopyranoside with 2, and subsequent O-deacetylation at O-4' gave a glycosyl acceptor, benzyl 2-acetamido-4-O-[2-acetamido-6-O-benzyl-3-O-(2-butenyl) -2-deoxy-beta-D-glucopyranosyl]-3,6-di-O-benzyl-2-deoxy-alpha-D-glucopyranoside .