Precision Cellulose from Living Cationic Polymerization of Glucose 1,2,4-Orthopivalates

Abstract

Cellulose serves as a sustainable biomaterial for a wide range of applications in biotechnology and materials science. While chemical and enzymatic glycan assembly methods have been developed to access modest quantities of synthetic cellulose for structure−property studies, chemical polymerization strategies for scalable and well-controlled syntheses of cellulose remain underdeveloped. Here, we report the synthesis of precision cellulose via living cationic ring-opening polymerization (CROP) of glucose 1,2,4-orthopivalates. In the presence of dibutyl phosphate as an initiator and triflic acid as a catalyst, precision cellulose with well-controlled molecular weights, defined chain-end groups, and excellent regio-and stereospecificity was readily prepared. We further demonstrated the utility of this method through the synthesis of precision native D-cellulose and rare precision L-cellulose.

Chemically Recyclable Pseudo-Polysaccharides from Living Ring-Opening Polymerization of Glucurono-1,6-lactones

“…Chemists have resorted to chemical synthesis to overcome these limitations and meet the demand for structurally homogeneous polysaccharides that can be tailored for advanced applications, such as glycobiology and drug delivery. Various synthetic approaches, including enzymatic synthesis, , polycondensation, − iterative assembly, − and ring-opening polymerization (ROP), , have been employed. Nevertheless, the high complexity and structural diversity of polysaccharides, in terms of functional groups and stereochemistry, must be carefully considered. , This often hampers the aforementioned techniques, making the development of new synthetic methods for precision polysaccharides a significant challenge.…”