Enzymes are indispensable tools in modern organic synthesis. Recent progres
s in cloning techniques, microbiology and protein purification supply an ev
er growing number and quantity of preparatively useful biocatalysts. initia
lly used to synthesize compounds found in nature, enzymes are now probed on
non-natural substrates to an increasing degree. They work on highly functi
onal and unprotected substrates under mild and environmentally friendly con
ditions. In addition, they exhibit an excellent chemo-, regio- and stereose
lectivity. The following article will focus on the application of glycosylt
ransferases in the area of molecular glycobiology. Selected reactions with
non-natural substrates will be discussed.