Enzyme catalyzed reactions are green alternative approaches to functionalize polymers compared to conventional methods. This technique is especially advantageous due to the high selectivity, high efficiency, milder reaction conditions, and recyclability of enzymes. Selected reactions can be conducted under solventless conditions without the application of metal catalysts. Hence this process is becoming more recognized in the arena of biomedical applications, as the toxicity created by solvents and metal catalyst residues can be completely avoided. In this review we will discuss fundamental aspects of chemical reactions biocatalyzed by Candida antarctica lipase B, and their application to create new functionalized polymers, including the regio- and chemoselectivity of the reactions.

The use of enzymes as catalysts for organic synthesis has become an increasingly attractive alternative to conventional chemical catalysis. Enzymes offer several advantages including high selectivity, ability to operate under mild conditions, catalyst recyclability, and biocompatibility. Although there are many examples in the literature involving enzymes for the synthesis of polymers, our search showed that very little had been done in the area of polymer modification. In this article, we will discuss enzyme catalysis in general and highlight our recent results concerning precision polymer functionalization using enzymatic catalysis—“green polymer chemistry.” © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 2959–2976, 2009