Liu C M, Warren C D, Jeanloz R W
Carbohydr Res. 1985 Feb 28;136:273-84. doi: 10.1016/0008-6215(85)85203-4.
2-O-Acetyl-3-O-allyl-4-O-benzyl-6-O-tert-butyldiphenylsilyl-D-gluc opyranosyl chloride (14), a glycosyl donor suitable for synthesis of oligosaccharides corresponding to the N-glycoprotein saccharide "core", was synthesized by an efficient, six-stage route from 3,4,6-tri-O-acetyl-1,2-O-[1-(exo-ethoxy)ethylidene)-alpha-D-glucopyranos e. Silver triflate-promoted coupling of 14 with benzyl 2-acetamido-3,6-di-O-benzyl-2-deoxy-alpha-D-glucopyranoside gave a protected beta-D-(1----4)-linked disaccharide in 38% yield, but a major side-reaction also occurred. When the tert-butyldiphenylsilyl group was quantitatively removed from 14 prior to the coupling reaction, and replaced afterwards, the yield in the glycosidation was increased to 55%, and major side-products were avoided.
2-O-乙酰基-3-O-烯丙基-4-O-苄基-6-O-叔丁基二苯基甲硅烷基-D-吡喃葡萄糖基氯（14）是一种适合用于合成与N-糖蛋白糖“核心”相对应的寡糖的糖基供体，它是由3,4,6-三-O-乙酰基-1,2-O-[1-（外-乙氧基）亚乙基]-α-D-吡喃葡萄糖通过一条高效的六步路线合成的。三氟甲磺酸银促进14与苄基2-乙酰氨基-3,6-二-O-苄基-2-脱氧-α-D-吡喃葡萄糖苷的偶联反应，得到了产率为38%的受保护的β-D-（1→4）连接的二糖，但同时也发生了一个主要的副反应。当在偶联反应之前将14中的叔丁基二苯基甲硅烷基定量除去，然后再进行取代时，糖基化反应的产率提高到了55%，并且避免了主要副产物的生成。
