Meppen Malte, Wang Yonghui, Cheon Hwan-Sung, Kishi Yoshito
Department of Chemistry and Chemical Biology, Harvard University, 12 Oxford Street, Cambridge, Massachusetts 02138, USA.
J Org Chem. 2007 Mar 16;72(6):1941-50. doi: 10.1021/jo061990v. Epub 2007 Feb 3.
With the hope of mimicking the chemical and biological properties of natural 6-O-methyl-D-glucose-containing polysaccharides (MGPs), synthetic 6-O-methyl-D-glucose-containing polysaccharides (sMGPs) were designed and synthesized from alpha-, beta-, and gamma-cyclodextrins (CDs). The synthetic route proved to be flexible and general, to furnish a series of sMGPs ranging from 6-mer to 20-mer. A practical and scalable method was discovered selectively to cleave the CD derivatives and furnish the linear precursors to the glycosyl donors and acceptors. The Mukaiyama glycosidation was adopted to couple the glycosyl donors with the glycosyl acceptors. Unlike in the 3-O-methyl-D-mannose-containing polysaccharide (sMMP) series, the amount of the Mukaiyama acid required in the sMGP series increased with an increase of substrate size; that is, for large oligomers, more than one equivalent of the acid was required.
为了模拟天然含6-O-甲基-D-葡萄糖的多糖（MGPs）的化学和生物学性质，从α-、β-和γ-环糊精（CDs）设计并合成了合成含6-O-甲基-D-葡萄糖的多糖（sMGPs）。合成路线被证明是灵活且通用的，可提供一系列从六聚体到二十聚体的sMGPs。发现了一种实用且可扩展的方法来选择性地切割CD衍生物，并提供糖基供体和受体的线性前体。采用Mukaiyama糖苷化反应将糖基供体与糖基受体偶联。与含3-O-甲基-D-甘露糖的多糖（sMMP）系列不同，sMGP系列中所需的Mukaiyama酸的量随着底物尺寸的增加而增加；也就是说，对于大的寡聚物，需要超过一当量的酸。
