Kobayashi M, Yamazaki F, Ito Y, Ogawa T
Riken (The Institute of Physical and Chemical Research), Saitama, Japan.
Carbohydr Res. 1990 Jun 15;201(1):51-67. doi: 10.1016/0008-6215(90)84224-i.
A stereocontrolled synthesis of beta-D-GlcpNAc6SO3-(1----3)-beta-D-Galp6SO3-(1----4)-beta-D- GlcpNAc6SO3- (1----3)-D-Galp, was achieved by use of benzyl O-(2-acetamido-3,4 di-O-benzyl-2-deoxy-6-O-p-methoxyphenyl-beta-D- glucopyranosyl)-(1----3)-O-(2,4-di-O-tert-butyldiphenylsilyl-beta- D- galactopyranosyl-(1----4)-O-(2-acetamido-3-O-benzyl-2-deoxy-6-O-p-methox yphenyl - beta-D-glucopyranosyl)-(1----3)-2,4,6-tri-O-benzyl-beta-D-galactopyranos ide as a key intermediate, which was in turn prepared by employing two glycosyl donors, 3,4-di-O-benzyl-2-deoxy-6-O-p-methoxyphenyl-2-phthalimido-beta-D- glucopyranosyl trichloroacetimidate and O-(3,6-di-O-acetyl-2,4-di-O-benzyl-beta-D-galactopyranosyl)-(1----4)-3-O - benzyl-2-deoxy-6-O-p-methoxyphenyl-2-phthalimido-beta-D-glucopyranosyl trichloroacetimidate, and a glycosyl acceptor, benzyl 2,4,6-tri-O-benzyl-beta-D-galactopyranoside.
通过使用苄基O-(2-乙酰氨基-3,4-二-O-苄基-2-脱氧-6-O-对甲氧基苯基-β-D-吡喃葡萄糖基)-(1→3)-O-(2,4-二-O-叔丁基二苯基甲硅烷基-β-D-吡喃半乳糖基-(1→4)-O-(2-乙酰氨基-3-O-苄基-2-脱氧-6-O-对甲氧基苯基-β-D-吡喃葡萄糖基)-(1→3)-2,4,6-三-O-苄基-β-D-吡喃半乳糖苷作为关键中间体，实现了β-D-GlcpNAc6SO3-(1→3)-β-D-Galp6SO3-(1→4)-β-D-GlcpNAc6SO3-(1→3)-D-Galp的立体控制合成，而该关键中间体又是通过使用两种糖基供体，即3,4-二-O-苄基-2-脱氧-6-O-对甲氧基苯基-2-邻苯二甲酰亚氨基-β-D-吡喃葡萄糖基三氯乙酰亚胺酯和O-(3,6-二-O-乙酰基-2,4-二-O-苄基-β-D-吡喃半乳糖基)-(1→4)-3-O-苄基-2-脱氧-6-O-对甲氧基苯基-2-邻苯二甲酰亚氨基-β-D-吡喃葡萄糖基三氯乙酰亚胺酯，以及一种糖基受体，苄基2,4,6-三-O-苄基-β-D-吡喃半乳糖苷制备而成的。
