Synthetic Studies of the Cororubicin Oligosaccharide: Glycosylation of Branched Amino and Nitro Sugars

Abstract Derivatives of the branched amino sugar methyl 3-amino-2,3,6-trideoxy-3-C-methyl-α-L-ribo-hexopyranoside and its 3-nitro analog were coupled with glycosyl donors of 3,4-di-O-acetyl-2,6-dideoxy-L-fucopyranose. Successful glycosylations were developed using the fucosyl bromide, activated with silver triflate, and the fucosyl oxysilane, activated with trimethylsilyl triflate. High stereoselectivities for the desired α-1,4 linkage were observed in both cases. The N-trifluoroacetamido disaccharide was deacylated and the amino group oxidized to nitro with dimethyldioxirane. An alternate route based on coupling of the fucosyl bromide with the nitro sugar methyl α-L-decilonitroside also gave the α-linked disaccharide, which is related to oligosaccharides found in the antibiotics cororubicin and arugomycin.

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