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Carbohydr Res. 1988 Mar 15;174:265-78.

Synthesis of a close analog of the repeating unit of the antifreeze glycoproteins of polar fish.

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  • 1Department of Biochemistry, College of Agricultural and Life Sciences, University of Wisconsin, Madison 53706.


The protected glycopeptide N-(benzyloxycarbonyl)-L-alanyl-[O-(2,3,4,6-tetra-O-benzoyl-beta-D- galactopyranosyl)-(1----3)-O-(2,4,6-tri-O-benzyl-alpha-D-galactopyranosy l)- (1----3)]-L-threonyl-L-alanine 2,2,2-trichloroethyl ester was made by coupling the respective disaccharide and tripeptide blocks. The disaccharide block was generated by coupling tetra-O-benzoyl-alpha-D-galactopyranosyl bromide to allyl 2,4,6-tri-O-benzyl-alpha-D-galactopyranoside and converting the product into O-(2,3,4,6-tetra-O-benzoyl-beta-D-galactopyranosyl)-(1----3)-2,4,6-tri-O -benzyl - alpha-D-galactopyranosyl chloride via the 1-propenyl glycoside and the free (1-OH) sugar. Alternatively, the 1-propenyl intermediate was obtained directly by using 1-propenyl 2,4,6-tri-O-benzyl-alpha-D-galactopyranoside as the acceptor in the initial coupling reaction. An efficient 3-step synthesis of 10 was accomplished by the dibutyltin oxide-assisted, selective crotylation of allyl alpha-D-galactopyranoside at O-3, followed by benzylation and treatment of the product with potassium tert-butoxide. The N-benzyloxycarbonyl (Z) and N-tert-butoxycarbonyl (Boc) 2,2,2-trichloroethyl esters of Thr-Ala and Ala-Thr-Ala were formed by sequential coupling. The silver triflate-promoted glycosylation of the Z-protected dipeptide and tripeptide by 2,3,4,6-tetra-O-benzyl-alpha-D-galactopyranosyl chloride, and of the tripeptide by 6, proceeded with excellent alpha-stereoselectivity. From the disaccharide tripeptide 21, the carboxyl-deprotected and fully deprotected derivatives were prepared.

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