Chemical modification has become an indispensable means to tune/enhance properties of polysaccharides for specific applications. While conventional modification methods such as esterification or etherification have contributed to a majority of industrial polysaccharide products, these methods more often require harsh reaction conditions and are restricted to a limited range of functionalities. We thus explore mild, modular and efficient chemistries in the functionalization of cellulose esters. Olefin cross-metathesis (CM) between cellulosic polymers with terminal olefin side chains and a variety of CM partners has been demonstrated by our group to be such a pathway for synthesis of cellulose esters/ethers with a broad range of functionalities including carboxylic acid, alcohol, and carboxamide.1 Moreover, the α,β-unsaturation after the CM reaction, which may otherwise lead to crosslinking and can be eliminated by hydrogenation, can serve as a secondary handle for thiol-Michael addition (TM) of different thiols such as 2-mercaptoethanol and 3-mercaptopropionic acid. As both CM and TM are mild, efficient and more importantly modular, this double modification strategy provides access to an even more diverse range of cellulose derivatives under mild conditions, which can be used in applications including oral drug delivery. References 1. (a) Meng, X.; Edgar, K. J., Synthesis of amide-functionalized cellulose esters by olefin cross-metathesis. Carbohydr. Polym. 2015, 132, 565-573; (b) Meng, X.; Matson, J. B.; Edgar, K. J., Olefin cross-metathesis, a mild, modular approach to functionalized cellulose esters. Polym. Chem. 2014, 5 (24), 7021-7033; (c) Meng, X.; Matson, J. B.; Edgar, K. J., Olefin cross-metathesis as a source of polysaccharide derivatives: cellulose omega-carboxyalkanoates. Biomacromolecules 2014, 15 (1), 177-187; (d) Dong, Y.; Edgar, K. J., Imparting functional variety to cellulose ethers via olefin cross-metathesis. Polym. Chem. 2015, 6, 3816-3827

Double modification of cellulose esters by olefin cross-metathesis and thiol-Michael addition reaction

251st National Meeting (2016)

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