Baeyer-Villiger monooxygenases (BVMOs) are enzymes able to perform hig
hly regio- plus stereoselective nucleophilic and electrophilic biooxyg
enations on various substrates. The resultant chiral products (lactone
s and sulfoxides) can be valuable for the chemoenzymatic synthesis of
a wide range of useful compounds. Recent studies have provided a numbe
r of alternative active-site models that attempt to explain the exquis
ite and unusual selectivity of BVMOs. This article reviews some of the
established applications, and considers the merits of the various pre
dictive models.