Aromatic substrates are processed by toluene dioxygenase to their corresponding chiral arene cis-dihydrodiol derivatives, a reaction having no equivalent in the realm of traditional synthetic chemistry.  The application of this biocatalytic method to target-oriented synthesis has resulted in short, enantioselective syntheses of a number of natural products such as pancratistatin, morphine alkaloids, carbohydrates, and unnatural analogues of these biologically active compounds.  Recent examples highlighting the utility of cis-dihydrodiols in synthesis will be presented along with new directions for a program in environmentally benign synthesis.
Additional applications of enzymatic methodology, in particular the resolution of β-ketoamides via yeast mediated reductions, will be discussed.