Melean Luis G, Love Kerry R, Seeberger Peter H
Department of Chemistry, Massachusetts Institute of Technology, Cambridge, MA 02139, USA.
Carbohydr Res. 2002 Nov 19;337(21-23):1893-916. doi: 10.1016/s0008-6215(02)00299-9.
Glucosamines are common components of many biologically important oligosaccharides. Reported is a systematic evaluation of glucosamine phosphates and trichloroacetimidates as glycosylating agents for the efficient construction of beta-(1 --> 6) glucosamine linkages. A set of differentially protected glucosamine donors incorporating a host of amine protecting groups, including 2-phthaloyl, benzyloxycarbonyl (Z), trichloroetheoxycarbonyl (Troc) and trichloroacetyl (TCA) protective groups, were prepared. Donors were initially evaluated for reactivity and protecting group compatibility in a solution-phase study with a model 6-hydroxyl galactose acceptor. Based on these results, glucosamine donor 10 was selected for the solution-phase synthesis of a beta-(1 --> 6)-glucosamine pentasaccharide. Finally, building block 10 proved well suited for use in the automated solid-phase synthesis of a repeating unit trisaccharide. An assessment of glucosamine phosphate donors as potential glycosylating agents for a variety of glucosamine linkages is also discussed.
氨基葡萄糖是许多具有重要生物学意义的寡糖的常见组成部分。本文报道了对磷酸氨基葡萄糖和三氯乙酰亚胺酯作为糖基化试剂用于高效构建β-(1→6)氨基葡萄糖连接的系统评价。制备了一组含有多种胺保护基的不同保护的氨基葡萄糖供体，包括2-邻苯二甲酰基、苄氧羰基（Z）、三氯乙氧羰基（Troc）和三氯乙酰（TCA）保护基。在与模型6-羟基半乳糖受体的溶液相研究中，首先评估了供体的反应性和保护基兼容性。基于这些结果，选择氨基葡萄糖供体10用于溶液相合成β-(1→6)-氨基葡萄糖五糖。最后，构建单元10被证明非常适合用于重复单元三糖的自动化固相合成。本文还讨论了磷酸氨基葡萄糖供体作为各种氨基葡萄糖连接的潜在糖基化试剂的评估。
