6'-α-麦芽糖基-麦芽三糖的化学合成，一种代表淀粉分支点的支链寡糖。

Chemical synthesis of 6'-alpha-maltosyl-maltotriose, a branched oligosaccharide representing the branch point of starch.

作者信息

Motawia M S, Olsen C E, Enevoldsen K, Marcussen J, Møller B L

机构信息

Department of Plant Biology, Royal Veterinary and Agricultural University, Copenhagen, Denmark.

出版信息

Carbohydr Res. 1995 Nov 7;277(1):109-23. doi: 10.1016/0008-6215(95)00203-6.

DOI:10.1016/0008-6215(95)00203-6

PMID:8548783

Abstract

Chemical synthesis of the branched pentasaccharide 6'-alpha-maltosyl-maltotriose (15) is reported, based on the use of one synthon as a glycosyl acceptor and another synthon as a glycosyl donor. The synthon used as glycosyl acceptor was phenyl 2,3,6-tri-O-benzyl-1-thio-beta-D-glucopyranoside (7) and was synthesized from D-glucose with phenyl 2,3-di-O-acetyl-4,6-O-benzylidene-1-thio-beta-D-glucopyranoside and phenyl 2,3-di-O-benzyl-4,6-O-benzylidene-1-thio-beta-D-glucopyranoside as key intermediates. The synthon used as glycosyl donor was O-(2,3,4,6-tetra-O-benzyl-alpha-D-glucopyranosyl)-(1-->4)-O-(2,3,6-tri-O -benzyl - alpha-D-glucopyranosyl)-(1-->6)-O-[(2,3,4,6-tetra-O-benzyl-alpha-D- glucopyranosyl)-(1-->4)]-2,3-di-O-benzyl-alpha,beta-D-glucopyranosyl trichloroacetimidate (12) and was synthesized from phenyl O-2,3,4,6-tetra-O-benzyl-alpha-D-glucopyranosyl)-(1-->4)-O-(2,3,6-tri-O- benzyl- alpha-D-glucopyranosyl)-(1-->6)-O-[(2,3,4,6-tetra-O-acetyl-alpha-D- glucopyranosyl)-(1-->4)]-2,3-di-O-acetyl-1-thio-beta-D-glucopyranoside with O-(2,3,4,6-tetra-O-benzyl-alpha-D-glucopyranosyl)-(1-->4)-O-(2,3,6-tri-O - benzyl-alpha-D-glucopyranosyl)-(1-->4)]-2,3-di-O-benzyl-D-glucopyranose as an intermediate. Condensation of compounds 7 and 12 followed by removal of the phenylthio group and debenzylation provided the branched pentasaccharide 15. Alternatively, the branched pentasaccharide was produced from amylopectin by consecutive alpha- and beta-amylase treatments and purified by chromatography. The identity of the products obtained by chemical synthesis and enzymatic hydrolysis is documented by 1H and 13C NMR spectra.

摘要

报道了基于使用一种合成子作为糖基受体和另一种合成子作为糖基供体的支链五糖6'-α-麦芽糖基-麦芽三糖（15）的化学合成。用作糖基受体的合成子是苯基2,3,6-三-O-苄基-1-硫代-β-D-吡喃葡萄糖苷（7），它由D-葡萄糖以苯基2,3-二-O-乙酰基-4,6-O-亚苄基-1-硫代-β-D-吡喃葡萄糖苷和苯基2,3-二-O-苄基-4,6-O-亚苄基-1-硫代-β-D-吡喃葡萄糖苷作为关键中间体合成。用作糖基供体的合成子是O-(2,3,4,6-四-O-苄基-α-D-吡喃葡萄糖基)-(1→4)-O-(2,3,6-三-O-苄基-α-D-吡喃葡萄糖基)-(1→6)-O-[(2,3,4,6-四-O-苄基-α-D-吡喃葡萄糖基)-(1→4)]-2,3-二-O-苄基-α,β-D-吡喃葡萄糖基三氯乙酰亚胺酯（12），它由苯基O-2,3,4,6-四-O-苄基-α-D-吡喃葡萄糖基)-(1→4)-O-(2,3,6-三-O-苄基-α-D-吡喃葡萄糖基)-(1→6)-O-[(2,3,4,6-四-O-乙酰基-α-D-吡喃葡萄糖基)-(1→4)]-2,3-二-O-乙酰基-1-硫代-β-D-吡喃葡萄糖苷与O-(2,3,4,6-四-O-苄基-α-D-吡喃葡萄糖基)-(1→4)-O-(2,3,6-三-O-苄基-α-D-吡喃葡萄糖基)-(1→4)]-2,3-二-O-苄基-D-吡喃葡萄糖作为中间体合成。化合物7和12缩合，随后除去苯硫基并脱苄基，得到支链五糖15。或者，通过连续的α-淀粉酶和β-淀粉酶处理从支链淀粉制备支链五糖，并通过色谱法纯化。通过化学合成和酶促水解获得的产物的同一性通过1H和13C NMR光谱证明。