Unexpected stereochemical outcome of activated 4,6-O-benzylidene derivatives of the 2-deoxy-2-trichloroacetamido-D-galacto series in glycosylation reactions during the synthesis of a chondroitin 6-sulfate trisaccharide methyl glycoside

被引:46
作者
Bélot, F [1 ]
Jacquinet, JC [1 ]
机构
[1] Univ Orleans, UFR, Fac Sci,Inst Chim Organ & Analyt, CNRS,UPRES A 6005, F-45067 Orleans, France
关键词
glycosylation reactions; 2-deoxy-2-trichloroacetamido-D-galactose derivatives; chondroitin 6-sulfate trisaccharide;
D O I
10.1016/S0008-6215(99)00322-5
中图分类号
Q5 [生物化学]; Q7 [分子生物学];
学科分类号
071010 ; 081704 ;
摘要
The synthesis of methyl (beta-D-glucopyranosyluronic acid)-(1 --> 3)-(2-acetamido-2-deoxy-6-O-sulfonato-beta-D-galactopyranosyl)-(1 --> 4)-(beta-D-glucopyranosid)uronate trisodium salt, a chondroitin 6-sulfate trisaccharide derivative, is described. Loss of stereocontrol in glycosylation reactions involving activated 4,6-O-benzylidene derivatives of the 2-deoxy-2-trichloroacetamido-D-galacto series and D-glucuronic acid-derived accepters was highlighted. This drawback was overcome through the use of phenyl 3,4,6-tri-O-acetyl-2-deoxy-1-thio-2-trichloroacetamido-beta-D-galactopyranoside, which afforded the desired P-linked disaccharide derivative in high yield with an excellent stereoselectivity. This later was submitted to acid-catalyzed methanolysis, followed by benzylidenation, and condensed with methyl 2,3,4-tri-O-benzoyl-1-O-trichloroacetimidoyl-alpha-D-glucopyranuronate to afford the expected trisaccharide derivative. Subsequent transformation of the N-trichloroacetyl group into N-acetyl, mild acid hydrolysis, selective O-sulfonation at C-6 of the amino sugar moiety, and saponification afforded the target molecule as its sodium salt in high yield. (C) 2000 Elsevier Science Ltd. All rights reserved.
引用
收藏
页码:93 / 106
页数:14
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