Enzyme technology has significantly expanded in scope and impact over the p
ast 10 years to include organic transformations in non-traditional environm
ents. This is in part due to an increased understanding and capability of u
sing enzyme catalysis in a wide variety of organic solvents, at interfaces,
and at high temperatures and pressures. This review focuses on a relativel
y new but rapidly expanding research activity where in vitro enzyme catalys
is is used for the synthesis of non-natural polyesters and polycarbonates.
The inclination to use of enzymes for polymer synthesis has been fueled by
a desire to carry out these reactions in the absence of heavy metals, at lo
wer temperatures, and with increased selectivity. Aspects of this work that
include enzyme-catalyzed step-growth condensation reactions, chain-growth
ring-opening polymerizations, and corresponding transesterification of macr
omolecular substrates are discussed.