Lepage Mathieu L, Schneider Jérémy P, Bodlenner Anne, Compain Philippe
Laboratoire de Synthèse Organique et Molécules Bioactives, Université de Strasbourg/CNRS (UMR 7509), Ecole Européenne de Chimie, Polymères et Matériaux , 25 rue Becquerel, 67087 Strasbourg, France.
Institut Universitaire de France , 103 Bd Saint-Michel, 75005 Paris, France.
J Org Chem. 2015 Nov 6;80(21):10719-33. doi: 10.1021/acs.joc.5b01938. Epub 2015 Oct 26.
A modular strategy has been developed to access a diversity of cyclic and acyclic oligosaccharide analogues designed as prefunctionalized scaffolds for the synthesis of multivalent ligands. This convergent approach is based on bifunctional sugar building blocks with two temporarily masked functionalities that can be orthogonally activated to perform Cu(I)-catalyzed azide-alkyne cycloaddition reactions (CuAAC). The reducing end is activated as a glycosyl azide and masked as a 1,6-anhydro sugar, while the nonreducing end is activated as a free alkyne and masked as a triethylsilyl-alkyne. Following a cyclooligomerization approach, the first examples of close analogues of cyclodextrins composed of d-glucose residues and triazole units bound together through α-(1,4) linkages were obtained. The cycloglucopyranoside analogue containing four sugar units was used as a template to prepare multivalent systems displaying a protected d-mannose derivative or an iminosugar by way of CuAAC. On the other hand, the modular approach led to acyclic alkyne-functionalized scaffolds of a controlled size that were used to synthesize multivalent iminosugars.
已开发出一种模块化策略，用于获取多种环状和非环状寡糖类似物，这些类似物被设计为用于合成多价配体的预官能化支架。这种收敛方法基于具有两个暂时掩蔽官能团的双功能糖砌块，这些官能团可以被正交活化以进行铜（I）催化的叠氮化物-炔烃环加成反应（CuAAC）。还原端被活化成糖基叠氮化物并被掩蔽为1,6-脱水糖，而非还原端被活化成游离炔烃并被掩蔽为三乙基硅烷基-炔烃。采用环寡聚化方法，获得了由d-葡萄糖残基和通过α-(1,4)键连接在一起的三唑单元组成的环糊精紧密类似物的首批实例。含有四个糖单元的环葡萄糖苷类似物被用作模板，通过CuAAC制备展示受保护的d-甘露糖衍生物或亚氨基糖的多价体系。另一方面，模块化方法导致了具有可控尺寸的非环状炔烃官能化支架，这些支架被用于合成多价亚氨基糖。
