Polysaccharides are ubiquitous in nature, and play many critical roles in biology. As such, the synthesis of polysaccharides and of polymers mimicking the structure or function of polysaccharides is of keen interest in order to reveal structure-function relationships and to prepare biocompatible and biodegradable materials for research and commercial applications. Recent developments in polymerization methodologies are enabling the synthesis of polysaccharides and polysaccharide mimetics with a variety of structures and architectures. While there have been significant advances in overcoming the difficulties in controlling the regioselectivity and stereospecificity of glycosidic bond formation during polymerization, the development of efficient synthetic routes with general applicability to stereoregular and structurally complex polysaccharides remains a challenge. This review comprehensively describes the chemical polymerization methods to synthesize polysaccharides with different compositions and architectures (linear, branched, and hyperbranched) and the synthetic procedures to polysaccharide mimetics possessing, for example, amine linkages, amide linkages, and carbonate linkages. It begins with a discussion of the challenges and strategies for the synthesis of polysaccharides. We highlight the complexity observed in theses macromolecules due to the number and variety of stereo- and regio-types of glycosidic linkages present between monosaccharide residues. With regards to polysaccharide mimetics, we focus on polymers displaying important structural features present in natural polysaccharides, such as a rigid polymer backbone containing heterocyclic ring structures, short linkages with less than three atoms, as well as multiple hydroxyl groups. Both condensation polymerization and ring-opening polymerization are used to prepare linear polysaccharides, branched polysaccharides, hyperbranched polysaccharides, non-O-glycosidic linked polysaccharide mimetics, and pseudopolysaccharides. The review concludes with reflections and suggestions for future directions of investigation.

多糖在自然界无处不在，在生物学中起着许多关键作用。因此，为了揭示结构-功能关系并制备用于研究和商业应用的生物相容性和可生物降解的材料，多糖和模拟多糖的结构或功能的聚合物的合成引起了人们的强烈兴趣。聚合方法学的最新发展使得能够合成具有多种结构和构造的多糖和多糖模拟物。尽管在克服聚合过程中控制糖苷键形成的区域选择性和立体特异性方面的困难方面取得了重大进展，发展普遍适用于立体有规和结构复杂的多糖的有效合成路线仍然是一个挑战。这篇综述全面描述了合成具有不同组成和结构（线性，支化和超支化）的多糖的化学聚合方法，以及具有例如胺键，酰胺键和碳酸酯键的多糖模拟物的合成方法。首先讨论多糖合成的挑战和策略。由于在单糖残基之间存在的糖苷键的立体和区域类型的数量和种类，我们强调了在这些大分子中观察到的复杂性。关于多糖模拟物，我们专注于显示天然多糖中存在的重要结构特征的聚合物，例如含有杂环结构的刚性聚合物主链，少于三个原子的短键以及多个羟基。缩聚和开环聚合均用于制备线性多糖，支链多糖，超支链多糖，非O-糖苷连接的多糖模拟物和假多糖。审查总结了对未来研究方向的思考和建议。